Category: Class 12

Std 12 Political Science Chapter 2 Question Answer Key Concepts and Issues Since 1991: Globalisation Maharashtra Board

Balbharti Maharashtra State Board Class 12 Political Science Solutions Chapter 2 Key Concepts and Issues Since 1991: Globalisation Textbook Exercise Questions and Answers.

Class 12 Political Science Chapter 1 Key Concepts and Issues Since 1991: Globalisation Question Answer Maharashtra Board

Political Science Class 12 Chapter 1 Question Answer Maharashtra Board

1. (A) Choose the correct alternative and complete the following statements

Question 1.
In 1995, GATT was replaced by the
(a) WTO
(b) ECOSOC
(c) UNDP
(d) TRIPS
Answer:
(a) WTO

Question 2.
……………… refers to a company that operates in several countries but has a distinct home base
(a) Transnational Corporation
(b) Mixed Economy
(c) Multinational Company
(d) Liberalism
Answer:
(c) Multinational Company

(B) Find the odd word.

Question 1.
Mobile, Satellite, Internet, Gramophone.
Answer:
Gramophone (not functioning on modern technology)

(C) State the appropriate concept for the given statements.

Question 1.
The international agency dealing with international trade.
Answer:
World Trade Organization (WTO)

Question 2.
The companies that operate in several countries.
Answer:
Multi National Companies

(D) Identify the incorrect pair in every set and correct it.

Question 1.
(a) Nestle – Trans National Corporation
(b) Copyrights – Intellectual Property
(c) India – Capitalist Market Economy
Answer:
(c) USA – Capitalist Market Economy
OR India – Economic Liberalism (Mixed economy)

Question 2.
(a) Amnesty International – Human Rights
(b) Green Peace – Environmental Issues
(c) Chernobyl – Trade Agreement
Answer:
(c) Chernobyl – Nuclear disaster

2. State whether the following statements are true or false with reason.

Question 1.
Globalisation brought in the concept of market economy.
Answer:
This statement is True.
(i) During the Cold War, the economic systems followed by countries, depended upon their ideology. For e.g., most West European nations and the USA were free democracies and followed capitalist economy.

(ii) In the era of globalisation there is only ‘market economy’. However, the nature of market economy is determined by the countries ideology for e.g., China has a socialist market economy, West European nations are described as ‘welfare market economies’ and USA is considered as ‘capitalist market economy’.

(iii) In most countries, the State has with draws from economic activities and the private sector and profit motive has propelled the economy.

Question 2.
Non-state actors have become irrelevant in the age of globalisation.
Answer:
This statement is False.
(i) Good governance and the participatory State focus on the role of the civil society which includes non-state actors such as NGO’s.

(ii) International relations today, are not only between States but also include non-state actors. These sometimes also pose a challenge to the position of the State. Globalisation has made non-state actors relevant. This includes organisations which are beneficial e.g., NGO’s working for humanitarian issues as well as threatening organisations e.g., terrorist outfits.

3. Explain the correlation between the following.

Question 1.
Globalisation and culture
Answer:
Globalisation refers to the rapid spread of goods and services, technology and information, ideas and culture, trade and interactions across the world. It is the connection of different parts of the world resulting in the expansion of international cultural, informational, economic and political activities. Events in one part of the world have an impact on other parts of the world. Changes have taken place economically and culturally.

Today a ‘global cosmopolitan culture’ has emerged i.e movement of people across the world and public awareness of global issues. This is noticed in matters like values eg secularism, clothing food choices, ways of celebrating festivals, etc. There is international awareness of India’s rich cultural and historical heritage. Similarly, westernisation and urbanisation have influenced Indian society eg breakup of the traditional joint family and rise of individualism and materialism in the country.

Question 2.
GATT and WTO
Answer:
The General Agreement on Tariffs and Trade (GATT) was signed on 30th October 1947 by 23 countries with the purpose to promote international trade by reducing/eliminating trade barriers such as tariffs or quotas. It came into force on 1st January 1948. It aimed to boost economic recovery after World War II through reconstructing and liberalizing global trade. It introduced the most favoured nation principle. GATT was refined over 8 rounds of negotiations, leading to creation of World Trade Organization (WTO) which replaced GATT on 1st January 1995.

WTO covers services and intellectual property also. It is the international agency overseeing the rules of international trade i.e., it promotes free trade agreements, organizes trade negotiations, settles trade disputes, etc. It’s headquarters is in Geneva. It has 123 member States. The WTO dispute settlement system is faster, more automatic than the GATT system and it’s rulings cannot be blocked.

4. Express your opinion of the following.

Question 1.
Participatory State is beneficial to the society.
Answer:
Participatory State advocates more involved forms of citizen participation and greater political representation than traditional representative democracy. It goes beyond traditional democratic practices wherein decisions are made by the majority. In a participatory State, all sections of the society are involved in the making of policy. Participatory State is beneficial as it gives citizens a central role in public policy through public discussion, negotiations, voting, etc. It emphasizes the importance of making citizens aware and providing for a form of communication which promotes political dialogue.

5. Answer the following question in 80 to 100 words.

Question 1.
What are the positive and negative aspects of Globalisation?
Answer:
Globalisation refers to the rapid spread of goods and services, technology and information, ideas and culture, trade and interactions across the world. It is the connection of different parts of the world resulting in the expansion of international cultural, informational, economic and political activities. In the early 1990s, the term globalisation was used to include economic, political, socio¬cultural, technological and ideological changes that occurred in the world in the post cold war era. The world has become more interconnected due to advances in technology and communication. Events in one part of the world have an impact on other parts of the world. Changes have taken place economically and culturally.

The Positive aspects of globalisation are-

1. It creates more employment opportunities.
2. It encourages free trade.
3. It leads to better choice of goods and services to the consumer.
4. It leads to wider investments in developing countries.
5. It enhances efficiency of the tertiary sector i.e., banking and finance.
6. It increases purchasing power of citizens and enhances their standard of living.
7. It increases labour productivity and reduces capital-output ratio.
8. It helps to increase efficiency in the production system.

The negative aspects of globalisation are-

1. Globalization promotes technological adaption to increase productivity but has also resulted in loss of jobs.
2. Local/small scale industries cannot withstand competition from the MNC’s and may be bought off or shut down.
3. Less developed countries may become dependent on the technologically superior countries.
4. It has caused specialization of labour and so there are few employment opportunities for unskilled labour.
5. It has led to increased gap between rich and poor nations.
6. It may lead to overexploitation of resources and negatively impact the environment.
7. It leads to the harmful effects of consumerism.
8. It may lead to reduction in social welfare schemes in both developed and developing countries.

Activity

Talk to people of the older generation to find out what changes have taken place in the age of globalisation.

Class 12 Political Science Chapter 2 Key Concepts and Issues Since 1991: Globalisation Intext Questions and Answers

Activity (Text Book Page No. 18)

Question 1.
What has been the impact of globalisation on the Indian agricultural sector, especially the small farmer?
Answer:
Globalisation has both positive and negative consequences on Indian agriculture.
The positive consequences are-
(i) Availability of modern agro technologies in pesticides / herbicides, fertilizers, new varieties of high yield seeds to increase food production.
(ii) There are new markets for agricultural products.
(iii) Farmers can sell their goods directly to companies and eliminate the role of middlemen.

The negative effects of globalisation on agriculture are-

1. Farmers are shifting from traditional / mixed cropping to unsustainable cropping practices mainly for cash crops.
2. MNC’s have captured the India market, making farmers dependent on expensive HYV seeds, fertilizers, etc.
3. Small and marginal farmers may not be able to avail of the advantages of globalisation. They may be pushed into debt leading to tragic consequences like farmer suicides.

Question 2.
Find out what the Arab Spring movement was and how social networking was used during that movement. (Text Book Page No. 21)
Answer:
Arab Spring was a series of protests and uprisings against the governments that spread across large parts of the Arab world in the early 2010s. (i.e. December 2010 to December 2012). It began with protests in Tunisia and spread quickly to other countries like Libya, Egypt, Yemen, Syria and Bahrain. There were riots, civil wars and the main slogan of protestors was “the people want to bring down the regime”.

There were sustained street demonstrations in Iraq, Algeria, Morocco, Jordan, Lebanon, etc. The social media i.e. facebook, etc. was the driving force behind the swift spread of the revolutions. The results of these movements were that regimes of Tunisia (Abidine Ben Ali), Egypt (Hosni Mubarak) Libya (Gaddafi), Yemen (Abdullah Saleh) were ousted while in Syria, Iraq, etc., a full scale civil war resulted. Only in Tunisia, there was a transition to constitutional democratic government.

Question 3.
Find out cases where agitations have used social networking to highlight their demands. (Text Book Page No. 21)
Answer:
Social networking and micro media have aided many protests and agitations. Some examples are:
(i) Arab Spring movements (2010-2012) used media power eg., Facebook to over throw despotic rulers e.g., Gaddafi in Libya or Hosni Mubarak in Egypt.

(ii) In India, the Anti-Corruption Movement led by Anna Hazare (2011) was helped by extensive media coverage and social media posts specially among the youth and students.

(iii) Social networking played a vital role in the “Me Too” movement all over the world to expose workplace sexual harassment especially in the glamour industry.

(iv) Social networking played a major role in galvanising support during the pro-democracy demonstrations in Hong Kong.

(v) Various social media handles fuelled the protests against NRC, CAA, etc., in various States of India.

Question 4.
Can the cooperative movement of India be an answer to the domination of multinational and transnational companies? The philosophy of the cooperative movement is to provide both, empowerment and finance to the members while that of the corporations work on profit motive. Give your opinion on this. (Text Book Page No. 17)
Answer:
Cooperative Movement in India can be traced to the Cooperative Credit Societies Act (1904). India’s first Prime Minister, Jawaharlal Nehru had strong faith in the cooperative movement. Hence, cooperatives became an integral part of Five Year Plans in India. In 1958, National Development council recommended setting up of Cooperative Marketing Societies. The major sectors where cooperatives dominate are in dairy, agriculture, banking and rural credit, etc. Article 43, Part IV (DPSP) of the constitution, mentions about promotion of cooperatives mainly in rural areas.

The importance of the cooperative sector.

• it provides agricultural credits where the State and private sectors have not been able to do so.
• it helps to overcome the constraints of agricultural development.
• it provides empowerment to the members.
• it can be an answer to the domination by the MNC’s which work solely on the profit motive. If the problems of cooperatives are overcome, they can strengthen the financial sector and lessen our reliance on MNC’s.

Maharashtra State Board 12th Std Political Science Textbook Solutions

• The World Since 1991 Class 12 Political Science Solutions
• Key Concepts and Issues Since 1991: Globalisation Class 12 Political Science Solutions
• Key Concepts and Issues Since 1991: Humanitarian Issues Class 12 Political Science Solutions
• Contemporary India: Challenges to Peace, Stability and National Integration Class 12 Political Science Solutions
• Contemporary India: Good Governance Class 12 Political Science Solutions
• India and the World Class 12 Political Science Solutions

Std 12 Geography Chapter 1 Question Answer Population Part 1 Maharashtra Board

Balbharti Maharashtra State Board Class 12 Geography Solutions Chapter 1 Population Part 1 Textbook Exercise Questions and Answers.

Class 12 Geography Chapter 1 Population Part 1 Question Answer Maharashtra Board

Geography Class 12 Chapter 1 Question Answer Maharashtra Board

1. Identify the correct correlation.

A – Assertion R – Reasoning
Question 1.
A – Areas which have fertile soil have dense population.
R – Fertile soils are good for agriculture.
(a) Only A is correct.
(b) Only R is correct.
(c) Both A and R are correct and R is the correct explanation of A.
(d) Both A and R are correct but R is not the correct explanation of A.
Answer:
(c) Both A and R are correct and R is the correct explanation of A.

Question 2.
A – Population of a region does not change.
R – Birth rate, death rate and migration affect the population of a region.
(a) Only A is correct.
(b) Only R is correct.
(c) Both A and R are correct and R is the correct explanation of A.
(d) Both A and R are correct but R is not the correct explanation of A.
Answer:
(b) Only R is correct.

Question 3.
A – In stage 2, death rate reduces but birth rate is constant.
R – Population increases rapidly in stage 2.
(a) Only A is correct.
(b) Only R is correct.
(c) Both A and R are correct and R is the correct explanation of A.
(d) Both A and R are correct but R is not the correct explanation of A.
Answer:
(c) Both A and R are correct and R is the correct explanation of A.

Question 4.
A – In stage 5 death rate is more than birth rate.
R – Population is declining in stage 5.
(a) Only A is correct.
(b) Only R is correct.
(c) Both A and R are correct and R is the correct explanation of A.
(d) Both A and R are correct but R is not the correct explanation of A.
Answer:
(c) Both A and R are correct and R is the correct explanation of A.

Question 5.
A – In stage 1 both death rate and birth rate are high.
R – Population growth is stable in stage 1.
(a) Only A is correct.
(b) Only R is correct.
(c) Both A and R are correct and R is the correct explanation of A.
(d) Both A and R are correct but R is not the correct explanation of A.
Answer:
(c) Both A and R are correct and R is the correct explanation of A.

2. Write short notes on.

Question 1.
Impact of relief on population distribution.
Answer:
1. Relief is one of the most important factors influencing the distribution of population.

2. Generally, mountains are thinly populated, plains are thickly populated and plateaus are moderately populated.

3. The mountains and hilly areas are less populated because of limited means of livelihood; agriculture is poorly developed and transportation facilities are limited. For example, north eastern states of India have less population due to hilly and mountainous relief.

4. On the other hand, plains are densely populated because of fertile soil and well-developed agriculture. Due to plain relief, it is easy to construct roads and develop industries. Better employment facilities attract people in these areas. For example, Ganga plains are thickly populated.

5. In short, we can say plains are densely populated and mountains and plateaus are sparsely populated.

Question 2.
Correlation between birth rate and death rate.
Answer:

• Birth rate and death rate are the important components of population change.
• Birth rate is the number of live births in a year per thousand population.
• Death rate is the number of deaths in a year per thousand population.
• Population growth depends upon birth rate and death rate in a year.
• Population growth occurs not only by increasing birth rate but also because of decreasing death rate.
• When birth rate is more than death rate, population increases.
• When birth rate is less than death rate, population decreases.
• If both, birth rate and death rate is same then population is said to remain stable. However, the birth rate and death rate being same is only a hypothetical situation.

Question 3.
Stage 3 of Demographic Transition Theory.
Answer:
1. Stage 3 of Demographic Transition Theory is the stage of expanding population.

2. From second stage to this stage, death rates are decreasing. Birth rates are also decreasing. Decrease in both birth rates and death rates, reduces the rate of growth of population. But actually, population is growing because the birth rates are higher than death rates.

3. In this stage, since the country is making progress, the income of the people is above the subsistence level and there is an improvement in the standard of living of the people. Poverty is also reducing.

4. There is development of technology as a result secondary and tertiary activities develop.

5. Due to increase in education level, people understand the importance of family planning so size of family reduces.

6. In short in stage 3 countries are moving from developing stage to developed stage.

3. Give geographical reasons.

Question 1.
India is passing through Stage 3 of demographic transition.
Answer:

• In India, since there is a decrease in the birth rates and death rates, the growth rate of population is also decreasing.
• Due to the development in the country, income of the people has reached above subsistence level, standard of living is improved, poverty is decreasing, technology is developing.
• Number of people engaged in secondary and tertiary activities are increasing.
• Due to increase in the literacy rate, people have understood the importance of family planning. Therefore, there is a decrease in the size of family.
• Hence, India is passing through Stage 3 of demographic transition.

Question 2.
Population distribution is uneven.
Answer:
1. Distribution of population in the world is very uneven because distribution of population depends upon many physical factors such as relief, climate, availability of water supply, soil etc.

2. For example, if you consider relief factor, mountains and hilly areas are thinly populated. Plateau regions are moderately populated and plains are densely populated. The Himalayan region in India is thinly populated but the Gangatic plains are thickly populated and Deccan plateau region are moderately populated.

3. The distribution of population also depends upon human factors such as agriculture, mining, transportation, urbanisation etc.

4. For example, agriculture or mining activities support large population since they provide source of living to many people.

5. Sometimes government policies also affect population distribution. For example, government provided land, water, electricity at concessional rate in New Mumbai area to attract people and to reduce pressure of population in Mumbai city.

Question 3.
Population increases because of transportation facilities.
Answer:
1. The development of roads and railways makes the region more accessible.

2. Such areas provide favourable conditions for the development and manufacturing industries, which generate employment. Therefore, people from different areas migrate in search of jobs. Thus, such areas become densely populated. For example, Gangetic plain of India, where the density of roads and railways is highest in India.

3. Population increases in port cities due to availability of sea transport for the development of trade. Therefore, the coastal region is densely populated. For example, many port cities like Chennai, Mumbai are developed on the east and west coast of India.

4. Thus, population increases because of transportation facilities.

Question 4.
Secondary and tertiary activities increase in the third stage of demographic transition.
Answer:

• In Stage 3 of demographic transition theory, growth rate of population decreases.
• As a result, the income of the people in the country reaches above subsistence level. Poverty rate decreases and standard of living increases. Therefore, the use of technology increases and this generates an employment in secondary and tertiary activities.
• Due to increase in education level and development of health facilities there is increase in employment in tertiary sector.
• Thus, secondary and tertiary activities increase in the third stage of demographic transition.

Question 5.
Population may increase though birth rates are low.
Answer:
The growth of population depends upon the difference between number of live births in a year per thousand population and number of deaths in a year per thousand population. Therefore, growth of population depends upon both birth rate and death rate.

When birth rate is low and death rate is also low, then though the number of live births per thousand population are less, but due to a smaller number of deaths per thousand population, there is increase in population of the country.

Question 6.
Population density is a function of population and area of a region.
Answer:
The number of people living in any area or country is called total population of the area or country.

Density of population is the ratio between total population and a total area of that region or country.

For example, as per the census of 2011, Density of population in India is 325 persons per sq. km. It is a ratio between total population in India and total area of India in sq. kms.

In some countries total population may be less but the density of population is high due to small area of the country. For example, Bangladesh’s total population is less but area of country is small therefore, density of population is high.

In some countries total population may be more but the density of population is low due to very large area of the country. For example, Brazil has more total population but area of country is also large therefore, density of population is low.

Thus, population density is a function of population and area of a region.

4. Answer the following questions in detail.

Question 1.
Explain the physical factors affecting distribution of population.
Answer:
Physical factors affecting distribution of population are:
(i) Relief
(ii) Climate
(iii) Availability of water
(iv) Soils

(i) Relief

• Distribution of population is greatly affected by relied features.
• Generally, flat plains or gently sloping lands are densely populated.
• Plains are suitable for agricultural activities.
• In these areas it is easier to construct roads and railways and development of industries and trade. As a result, many people are attracted to plains and they become densely populated. For example, Ganga plains are thickly populated.
• On the other hand, in mountainous and hilly areas density of population is low. This is because in such areas agricultural development is difficult.
• The construction and development of transport facilities is very difficult and costly too. Such areas are inaccessible.
• Due to inaccessibility, movement of goods and people are restricted. Therefore, mountainous and hilly areas are thinly populated. For example, north eastern states of India have less population due to hilly and mountainous relief.

(ii) Climate

• Climate is the most important factor of all the factors influencing the distribution of population.
• Areas having very hot or very cold climate, heavy rainfall are very uncomfortable for human settlement. Such areas are thinly populated.
• For example, polar regions where Eskimos and Lapps live are sparsely populated due to extreme cold climate. Sahara Desert is sparsely populated due to extreme hot climate.
• On the other hand, areas with equable climate, that is climate having not much seasonal variation attract people. People feel comfortable to stay in these areas.
• For example, coastal areas have dense population because of equable climate and wide scope for the development of agriculture, industries and trade.

(iii) Availability of water

• Water is the most important factor affecting distribution of population. It is the most essential factor for all human activities.
• Therefore, more people live in areas where potable and sufficient water is available. As a result of this most of the river valleys are densely populated i.e. Nile river valley.
• Even in desert areas there is more population near oasis due to availability of water.

(iv) Soil

• Fertile soils are most important for the development of agriculture.
• The areas having fertile alluvial soil have developed intensive agriculture and support large number of people and hence they are densely populated, e.g., Gangetic Plain, Plains of Mississippi, Irrawaddy and Yangtze etc.
• Similarly, in the areas having very fertile black cotton soil or regur soil, agriculture is well developed and hence such areas are densely populated.
• The volcanic soil is very fertile hence, it supports agriculture. Therefore, slopes of volcanic mountains have dense population. For example, volcanic mountain slopes of Java island.

Question 2.
In the first and fifth stage of the demographic transition, population growth is almost nil. What is the difference between the two stages then?
Answer:

• In the stage 1 both birth rates and death rates are high. The difference between the two is very less and therefore, population is stable.
• In stage 1 birth rates are high due to limited educational opportunities, people feel having many children is good. Therefore, families are big.
• In stage 1, due to lack of sanitation facilities, medical facilities, spread of contagious diseases, malnutrition, etc., death rate is high.
• In stage 5 birth rates and death rates are very low. Birth rates are almost equal to death rates.
• As a result, the population growth is almost minimal or very low or even negative in case of some countries.
• In stage 5, death rate is low because of improved medical facilities, eradication of contagious diseases and healthy environment.
• In stage 5, due to increase in awareness among the people, birth rate is low.

Question 3.
Discuss the problems faced by counties in stage 4 and stage 5.
Answer:
Problems faced by stage 4 countries are as under:

• The death rate is very low and going down as the medical facilities have improved and pandemic like plague, cholera, small pox, etc., are eradicated.
• Birth rate is the same as death rate so population growth is minimal.
• Problems faces by stage 5 countries are as under:
• In this stage the birth rate is very low and death rate is high. Therefore, the growth of population is slow or negative growth of population is seen.
• Due to large number of old people the death rate is high and due to a smaller number of young people birth rate is low.
• Due to large number of old people, dependent population is high.
• Due to less young age population, working population is limited.
• As a result, the size of dependant population is larger than active population and it has adverse effect on economy of the country.

5. Draw a neat labelled diagram for demographic transition theory and its various stages.
Answer:

6. Mark and name the following on the outline map of the world with suitable index.

(a) Highly populated region in Australia.
(b) Sparsely populated region in India.
(c) Any 2 countries in stage 5 of demography transition theory.
(d) Any 2 countries in stage 2 of demographic transition theory.
Answer:

Class 12 Geography Chapter 1 Population Part 1 Intext Questions and Answers

Try These

Question 1.
Observe the pie charts shown in the figure and answer the following questions. (Text book pg.no – 1)

1. Which continent has least population?
2. Which continent has the least landmass and also least population?
3. Which continent has the most land mass as well as most of the population?
4. Which continent is missing in one of the pie charts? Why?

Answer:

1. The continent which has the least population is Australia.
2. The continent which has the least land mass and also least population is Australia.
3. The continent which has the most land mass and also most population is Asia.
4. The continent of Antarctica is missing in population distribution chart, because it has no permanent human settlement.

Question 2.
Look at the below figure and answer the questions that follow:

1. What does the image show?
2. What happens to the population when the deaths are more than births?
3. What happens to the population when births are more than deaths?
4. What happens when both are same? Is it possible?

Answer:

1. The image shows balance between birth rate and death rate.
2. Population growth may be less or in some countries there may be negative growth.
3. When births are more than deaths, then population growth is faster.
4. When both births and deaths are same, population will be stagnant. This is not possible for any country.

Give it a try

Question 1.
The below table shows the 10 most populated countries in the world in 2018 with their areas. Calculate their population densities and complete the table. (Text book pg.no – 1)

Answer:

Question 2.
The satellite image given in Fig. They show the same area from two different periods. (Text book pg.no – 6)

1. What difference do you see?
2. What might have caused these changes?

Answer:
1. The satellite image ‘A’ is image of the year 2005 and satellite image ‘B’ is of the year 2019. That means there is a difference of 14 years in these two images.

2. In image ‘A’ you can see that there are a few roads, limited settlements and most of the areas are covered by agricultural fields, and there is thin population.

3. When we compare the image ‘A’ with the image ‘B’, we find that in image ‘B’ the number of major roads (highway) and minor roads have increased. As a result, the area has become more accessible and thickly populated.

Due to development of industries and employment opportunities there is development of transport.

Question 3.
1. Can you calculate the death rate if the total number of deaths in the above city was 2,986 in the same year?
2. On the basis of the birth rates given in earlier and death rates calculated, what change in population do you observe?
Answer:
1. Total population of a city is 223000 and total deaths in the city are 2986 in that year.
Death Rate = \(\frac {Total number of deaths in a year}{Total population in that year}\) × 1000
Death Rate = \(\frac {2896}{223000}\) × 1000 = 13.39
Therefore, the death rate is 13.39.

2. In earlier example birth rate was 14.57 and the death rates calculated is 13.39. It means death rate have decreased by 1.8. It means the population has increased.

Question 4.
Look at the graph in Fig. carefully. Answer the following questions: (Text book pg.no – 9)

1. What do the blue and black lines indicate?
2. What does the green part in the graph show?
3. What does the blue part in the graph show?
4. In which stages is the birth rate more than the death rate?
5. In which stages is the birth rate same as the death rate?
6. In which stage is the death rate being more than birth rate?

Answer:

1. Blue lines indicate birth rate and black lines indicate death rate.
2. Green part in the graph shows the natural increase of population.
3. Blue part in the graph shows the natural decrease of population.
4. In stage 2 and 3 birth rates is more than death rate.
5. In stage 4 the birth rate is same as the death rate.
6. In stage 5 the death rate is more than birth rate.

Make friends with maps!

Question 1.
Look at the map in Fig. Compare it with the physical map of the world given in Textbook Page No. 83. Try to understand the impact of physical factors on population distribution. Complete the table accordingly. (Text book pg.no – 2)


Answer:

Question 2.
Refer to the map showing rice producing regions of the world in Fig. Relate it with the population map of the world in Fig. Write the conclusions in your own words. (Text book pg.no – 5)


Answer:
Areas of high density of population in Fig 1.2 if we compare with world map Fig 1.4 showing major rice producing areas in the world, we found that the areas of major rice production and areas of high density / thick population are the same areas.
Conclusion:
Rice cultivation is possible only in those areas where there is fertile alluvial soil and assured supply of water.
Rice producing areas and areas of dense population in the world are the river flood plains and delta of rivers like Kaveri, Krishna, Godavari and Ganga in India, Brahmaputra in Bangladesh, Irrawaddy in Myanmar, Yangtze and Yellow in China, Mekong in Laos and Cambodia etc. These areas are high density areas in the world.

Can you tell?

Question 1.
Can you think of the factors besides physiography which affect the distribution of population? Make a list. (Text book pg.no – 3)
Answer:

Question 2.
Observe the table 1.4. Arrange data in ascending order for birth rate and death rates respectively. (Text book pg.no – 8)

Answer:

Question 3.
Look at the Fig. and answer the following questions. (Text book pg.no – 9)

1. If the crude birth rate is 7 and crude death rate is 8 then which stage of demographic transition is the country in?
2. If a country has crude death rate of 20 and crude birth rate of 24, then which stage of demographic transition is the country in? [Text book pg.no – 10]

Answer:

1. The country is in stage 5 of demographic transition.
2. The country is in stage 3 of demographic transition.

Find out.

Question 1.
(i) Are Eskimos still living in their conventional ways?
(ii) What changes can be seen in their lifestyle now? (Text book pg.no – 4)
Answer:
(i) No, Eskimos are not living in their conventional way due to the changing environment as a result of increased contacts with societies to the south.

(ii) Eskimo life has changed greatly because of increased contacts with societies to the south.

• They were using harpoons for hunting, now they are using rifles. They were using dogs for land transport, now they are using snowmobiles.
• Outboard motors, store-bought clothing and many other manufactured products have entered into their culture.
• Women are taking salaried jobs to earn currency for store-bought products. As a result, women are losing their knowledge of traditional skills such as sewing animal skin.
• Many Eskimos are not doing nomadic hunting which was their main activity. Now they are living in northern towns and cities and working in mines and oil fields.
• Some Eskimos in Canada have formed cooperative societies for marketing their handicrafts, fish catches, tourism ventures etc.

Use your brain power!

Question 1.
(i) Can lakes be a factor for concentration of population? Find examples.
(ii) Which water bodies are surrounded by dense population in Maharashtra? (Text book pg.no – 4)
Answer:
(i) Man always likes to settle near a waterbody. People are attracted towards lakes.

Lakes are not only a source of fresh water but also a source of fish. They also provide water supply for industries, agriculture and provide water transport. They provide good sites to develop tourism due to greenery of trees surrounding the lake, scope for boating, cool breeze and pleasant atmosphere.

For example, Lake Victoria in Africa, supports 40 million people, with population density 250 persons per sq. km. The growth rate of the population is 3.5 percent each year, which is among the highest growth rates in the world.

The Victoria lake supports the largest freshwater fishery in the world. The fish catch from the lake is more than one million and it employs two lakh people in direct fishing and supports livelihood to four million people.

Five Great lakes in USA – Superior, Huron, Michigan, Erie and Ontario make up the largest body of freshwater on earth. They support more than 30 million people. This equates to 10 percent of USA residents and 30 percent Canadian residents.

The lakes have been a major source for transportation, trade, fishing, tourism, power, recreation etc.

(ii)

• In Maharashtra the following water bodies are surrounded by dense populations.
• Rankala lake around which dense population of Kolhapur city.
• Powai lake around which dense population of Mumbai city.
• Ambazari lake around which dense population of Nagpur city.
• Pashan lake around which dense population of Pune city.
• Dense population on the bank of Mula-Mutha river of Pune city.
• Dense population on the bank of Nag river – Nagpur city.
• Dense population on the bank of Tapi river – Bhusaval and other cities.
• Dense population on the bank of Godavari river – Nasik city.
• Dense population on the bank of Krishna- Koyana rivers – Karad, Sangli cities.
• Dense population along the coastline of Arabian sea- Mumbai city.

Question 2.
In which stage do you think India is passing right now? (Text book pg.no – 10)
Answer:
India is passing through stage 3 right now.

Question 3.
Find out in what multiples has population increased in the following timeline and write down your findings. For example, in the initial phase, the population took 6 centuries (1000 to 1600 A.D.) to double itself. (Text book pg.no – 11)

Answer:
(i) 1000 to 1600 population increase 2 times in 6 hundred years.
(ii) 1600 to 1900 population increased 3 times in 3 hundred years.
(iii) 1900 to 1960 population increased 2 times in 6 hundred years.
(iv) 1960 to 2000 population increased 2 times in 4 hundred years.

Let’s recall.

Question 1.
Which policy did the Brazilian government promote with respect to decentralisation? (Text book pg.no – 7)
Answer:

1. Last two decades there is highly centralised military rule in Brazil so there was demand for local autonomy. Brazil sought to decentralised government authority and promote citizen participation to establish democracy.
2. Brazil became decentralised federation when it undertook transformation of governance.
3. As result authoritarian military regime came to an end.

Maharashtra State Board 12th Std Geography Textbook Solutions

• Population Part 1 Class 12 Geography Textbook Solutions
• Population Part 2 Class 12 Geography Textbook Solutions
• Human Settlements and Land Use Class 12 Geography Textbook Solutions
• Primary Economic Activities Class 12 Geography Textbook Solutions
• Secondary Economic Activities Class 12 Geography Textbook Solutions
• Tertiary Economic Activities Class 12 Geography Textbook Solutions
• Region and Regional Development Class 12 Geography Textbook Solutions
• Geography: Nature and Scope Class 12 Geography Textbook Solutions

Std 12 Political Science Chapter 1 Question Answer The World Since 1991 Maharashtra Board

Balbharti Maharashtra State Board Class 12 Political Science Solutions Chapter 1 The World Since 1991 Textbook Exercise Questions and Answers.

Class 12 Political Science Chapter 1 The World Since 1991 Question Answer Maharashtra Board

Political Science Class 12 Chapter 1 Question Answer Maharashtra Board

1. (A) Complete the following statements by selecting the appropriate option.

Question 1.
One of the important trends in post-1989 international relations was
(a) End of bipolarity
(b) Rise of regionalism in Asia
(c) End of non-alignment
(d) Demand for a new international economic order
Answer:
(a) End of bipolarity

Question 2.
The ‘Maastricht’ Treaty is with reference to
(a) United Nations Peace Keeping Force
(b) European Union
(c) American interventions in Kuwait
(d) Creation of BRICS
Answer:
(b) European Union

1. (B) State the appropriate concept for the given statements.

Question 1.
When a State influences other States without the use of military force.
Answer:
Soft power

Question 2.
A State with a leading position in international politics with abilities to influence global politics and fulfill its own interest.
Answer:
Super power

2. (A) Complete the concept maps.

Question 1.

Answer:

Question 2.

Answer:

2. (B) Observe the maps in the textbook and answer the following questions.

Question 1.
Name any four countries in the Schengen area.
Answer:
Sweden, Denmark, Germany, Belgium, France.

Question 2.
Name any two non-European Union countries within Schengen area.
Answer:
Norway, Romania, Bulgaria, Croatia.

3. State whether the following statements are true or false with reason.

Question 1.
SAARC is important for trade in South Asia.
Answer:
This statement is True.
(i) SAARC has eight member States from South Asia. It aims to accelerate economic growth and promote the welfare of the people of South Asia.
(ii) In 1993, South Asian Association for Preferential Trade Agreement (SAPTA) came into existence. It was replaced in 2006 by South Asian Association Free Trade Area (SAFTA). This helps in trade and economic activity in the region.

Question 2.
‘Maastricht’ Treaty was signed for the defence of Europe.
Answer:
This statement is False.
(i) On 7th February 1992, the Maastricht Treaty was signed to create the European Union.
(ii) This treaty led to the expansion of spheres of cooperation in internal affairs, foreign policies and defence policies.

Question 3.
The decade of 1980s is seen as the golden age of humanitarian intervention.
Answer:
This statement is False.
(i) The 1990s are seen as the ‘golden age of humanitarian intervention.’ In 1993, the World Conference on Human Rights was held in Vienna, which led to the creation of the office of UN High Commissioner for Human Rights.
(ii) Increasing awareness about human rights and their protection in international law gave rise to the phenomenon for protection of rights in the form of ‘humanitarian intervention’.

4. Express your opinion of the following.

Question 1.
Humanitarian intervention
Answer:
One of the main purposes of the UN is maintenance of international peace, security and cooperation. UN Peacekeeping Force comprises of military personnel and resources sent by member States. In the post-cold war era, the UN rationale for intervention was not just to stop ongoing wars but also to prevent reoccurrence of conflicts and protect the human rights of the affected people. The UN intervened in Cambodia, Somalia, Yugoslavia, East Timor, Eritrea, Syria, etc., for this purpose.

In 1993, over 170 nations participated in the World Conference on Human Rights, held in Vienna to reaffirm their commitment to protect human rights. The office of the UN High Commissioner for Human Rights was created to coordinate human rights initiatives. The increasing awareness about human rights protection in international law gave rise to humanitarian intervention especially in conflict zones. NGO’s have contributed significantly in the spread of humanitarian intervention for e.g. ICRC, Oxfam, etc. The 1990s are described as “golden age” of humanitarian intervention.

Question 2.
Regionalism in international politics.
Answer:
Countries which lie in geographical proximity create or join regional organisations which are based on common political, ideological, economic and infrastructural concerns. Some nations make special agreements regarding trade and economic cooperation. This is called a trade bloc.

(i) European Union (EU) was created in 1992 by Maastricht Treaty. It led to increased spheres of cooperation between European nations e.g. foreign affairs, defense, trade and creation of Euro as a common currency. Creation of Schengen Area is one of the achievements of the EU since the Schengen visa allows eligible individuals to travel freely within the 26 nations of the Schengen area.

(ii) ASEAN created in 1967 with headquarters at Jakarta comprises of 10 South-East Asian nations such as Brunei, Indonesia, Malaysia, Singapore, etc. It aims to promote political economic and security cooperation among it’s members.

(iii) SAARC formed in 1985 at Dhaka with 7 members. Today, it has 8 member countries of South Asia like India, Bhutan, Pakistan, etc. It aims to promote regional integration and economic development. It’s main achievement is the SAFTA.

(iv) BIMSTEC – is a regional organisation founded in 1997 comprising of 7 member countries lying around Bay of Bengal for e.g. Bangladesh, India, Thailand, Myanmar. It aims to facilitate collaboration in economic, security and other concerns between member States.

(v) Shanghai Cooperation Organisation (SCO) is an Eurasian political, economic and security organisation formed in 2001 with 6 member states. In 2016, India and Pakistan joined SCO. It’s focus is on maintaining peace and stability in the region, cooperation in trade, technology, etc.

Regional organisations play an important role in international politics. Due to this, unipolarity (US as the only superpower) ended leading to multipolarity.

5. Answer the Following.

Question 1.
Explain the term soft power with examples.
Answer:
According to American academic, Joseph Nye there are two types of power viz. hard power and soft power.
(i) Hard power is the ability to get others to act in ways that are contrary to their preferences and wills. It is the ability to coerce through threats and inducements for e.g.,Iraq invasion of Kuwait.

(ii) Soft power is when a country influences other countries without the use of military force. It is the ability to get others to want the outcomes that you want i.e. through attraction rather than coercion. Such influence is spread through economic, socio-cultural means.

Soft power was an important aspect of US domination. It implied the use of monetary aid, cooperative programmes, cultural exchanges, strong relations with allies. Examples of US soft power are cultural exports like fast food chains, movies, educational exchange programmes as well as disaster assistance programmes such as tsunami relief (Japan), flood control (Pakistan).

6. Answer the following question in detail with help of given points.

Question 1.
Discuss the European Union with help of given points.
(a) History
(b) European Commission
(c) European Parliament
(d) European Council
(e) European Court of Justice
Answer:
(a) History – The European Coal and Steel Community (ECSC) and European Economic Community (EEC) were created to foster economic interdependence. On 7th February 1992, the Maastricht Treaty was signed to create the European Union. This led to expansion of spheres of cooperation to include internal affairs, judicial matters, foreign policy, etc. The Euro (€) is the official currency of 19 out of 28 countries of the EU. These nations are collectively called ‘Eurozone’.

(b) European Commission – The Commission is the executive bureaucratic arm of the EU. It is mainly responsible for drawing up proposals for new European legislation,and it implements the policy decisions of the European Parliament and the Council of the EU.

(c) European Parliament – The European Parliament is composed of 751 Members, who are directly elected every five years. It is a body entrusted with legislative, supervisory, and budgetary responsibilities.

(d) European Council – The structure of the European Council consists of the Presidents or Prime Ministers of each member State, accompanied by their foreign ministers, and a full¬time President of the European Council. The European Council meets four times a year and provides strategic leadership for the EU.

(e) European Court of Justice (ECJ) – The ECJ interprets, and adjudicates on, EU law and treaties. As EU law has primacy over the national law of EU member States.

ACTIVITY

Find out the role played by India in BRICS (Text Book Page No. 13)
Answer:
BRICS refers to five major emerging national economies, i.e., Brazil, Russia, India, China and South Africa. It accounts for about 40% of the world’s population and 20% of the GDP. It is an emerging investment market and global power bloc. India serves a multi faceted role on the economic and political fronts.

(i) New Development Bank (NDB) was proposed by India during the BRICS summit in New Delhi. It was established in 2014 and intends to provide non conditional financing. India has contributed $ 10 billion to the NDB to refurbish industrial bases in Brazil and South Africa. There is a regional office of NDB in India.

(ii) In 2012, India introduced “security” on the agenda, as the theme of the summit in New Delhi was BRICS Partnership for Global Stability, Security and Prosperity.

(iii) India has also highlighted climate governance at BRICS meeting.

(iv) BRICS membership elevates India’s global profile for e.g., India has assumed the role of a trade facilitator in Africa and South Asia. It aims to promote intra-BRICS trade, which means urging member nations to import goods mainly from each other.

(v) India is seen as a strong voice at BRICS and the UN against proposals and actions that could harms any member’s interests for e.g., India turned down China’s proposal to invite Pakistan, Sri Lanka and Mexico into the BRICS to focus only on development within current members.

Class 12 Political Science Chapter 1 The World Since 1991 Intext Questions and Answers

ACTIVITY (Text Book Page No. 7)

Question 1.
What is One Belt One Road and China Pakistan Economic Corridor policy of China?
Answer:
One Belt One Road also called OBOR or Belt and Road Initiative (BRI) since 2016, is a global development strategy adopted by the Chinese government in 2013 involving infrastructure development and investments in nearly 70 countries in Asia, Europe and Africa. It is an ambitious economic development and commercial project that focuses on improving cooperation among multiple countries.

BRI involves building a network of roadways, railways, power grids, maritime ports, oil and gas pipelines and associated infrastructure projects. The project covers two parts i.e., Silk Road Economic Belt (land based) and expects to connect China with Central Asia, East and West Europe to connect China with Central Asia, East and West Europe) and 21st Century Maritime Silk Road (sea based and connects China to Africa, South East Asia, Mediterranean) BRI consists of six economic corridors such as China-Pakistan corridor, China- Indochina Peninsula corridor etc.

China-Pakistan Economic Corridor (CPEC) launched in 2015 is a part of the greater OBOR. It is a collection of infrastructure projects that are currently under construction throughout Pakistan for e.g., special economic zones, ports, energy projects, etc. The Gwadar Port (Balochistan province of Pakistan) which is considered the deepest seaport in the world is considered to be significant in the BRI. India has objected to the CPEC as upgrade works to the Karakoram Highway are taking place in Gilgit Baltistan (which is Indian territory) and will undermine India’s security and position in the region.

Question 2.
Who are the members of the European Union? (Text Book Page No.9)
Answer:
There are 27 countries who are members of European Union. These are Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden. UK was a member but left in January 2020.

The following countries are part of Eurozone.
Austria, Belgium, Cyprus, Estonia, Finland, France, Greece, Germany, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, the Netherlands, Portugal, Slovakia, Slovenia and Spain. The Eurozone is the monetary union of 19 out of 27 countries of the EU i.e., those who have Euro (€) as their common currency. The other 8 EU countries continue to use their national currencies.

Question 3.
Discuss the case of Brexit. (Text Book Page No. 11)
Answer:
British Exit i.e., Brexit is the withdrawal of the United Kingdom from the European Union. In June 2016, 52% voted to leave the EU following a UK wide referendum. The UK finally left the EU on 31st January 2020.
The main reasons for Brexit were-
(i) EU threatens British sovereignty and prevents radical reforms.
(ii) The Euro has been a disaster and caused the Greek economic crisis.
(iii) UK could have a more rational immigration system outside the EU as the EU allows too many immigrants.

Brexit is a rejection of globalisation. The European Union signified a move from a single market to a single currency, a single banking system and eventually a single political entity. Many persons argue that Brexit goes against the concept of globalisation, i.e., it symbolizes a protest against the economic model that has been in place since 1992.

Many voters feel that globalisation has benefited only a small elite and hanker for a return to the security provided by the nation-States i.e., jobs, living standards, welfare facilities seemed better protected in the nation-States prior to globalisation for e.g., unemployment across the Eurozone is more than 10% and Italy, Greece, etc., are facing economic crisis.

Maharashtra State Board 12th Std Political Science Textbook Solutions

• The World Since 1991 Class 12 Political Science Solutions
• Key Concepts and Issues Since 1991: Globalisation Class 12 Political Science Solutions
• Key Concepts and Issues Since 1991: Humanitarian Issues Class 12 Political Science Solutions
• Contemporary India: Challenges to Peace, Stability and National Integration Class 12 Political Science Solutions
• Contemporary India: Good Governance Class 12 Political Science Solutions
• India and the World Class 12 Political Science Solutions

Chemical Kinetics Class 12 Exercise Question Answers Solutions Maharashtra Board

Balbharti Maharashtra State Board 12th Chemistry Textbook Solutions Chapter 6 Chemical Kinetics Textbook Exercise Questions and Answers.

Class 12 Chemistry Chapter 6 Exercise Solutions Maharashtra Board

Chemistry Class 12 Chapter 6 Exercise Solutions

1. Choose the most correct option.

Question i.
The rate law for the reaction aA + bB → P is rate = k[A] [B]. The rate of reaction doubles if
a. concentrations of A and B are both doubled.
b. [A] is doubled and [B] is kept constant
c. [B] is doubled and [A] is halved
d. [A] is kept constant and [B] is halved.
Answer:
b. [A] is doubled and [B] is kept constant

Question ii.
The order of the reaction for which the units of rate constant are mol dm^-3 s^-1 is
a. 1
b. 3
c. 0
d. 2
Answer:
c. 0

Question iii.
The rate constant for the reaction 2N₂O₅(g) → 2N₂O₄(g) + O₂(g) is 4.98 × 10^-4 s^-1. The order of reaction is
a. 2
b. 1
c. 0
d. 3
Answer:
b. 1

Question iv.
Time required for 90 % completion of a certain first order reaction is t. The time required for 99.9 % completion will be
a. t
b. 2t
c. t/2
d. 3t
Answer:
d. 3t

Question v.
Slope of the graph ln[A]_t versus t for first order reaction is
a. -k
b. k
c. k/2. 303
d. -k/2. 303
Answer:
a. -k

Question vi.
What is the half life of a first order reaction if time required to decrease concentration of reactant from 0.8 M to 0.2 M is 12 h?
a. 12 h
b. 3 h
c. 1.5 h
d. 6 h
Answer:
d. 6 h

Question vii.
The reaction, 3ClO^3Θ ClO₃^Θ + 2 Cl^Θ occurs in two steps,
(i) 2 ClO^– → ClO₂^Θ
(ii) ClO₂^Θ + ClO^Θ → ClO₃^Θ + Cl^Θ

The reaction intermediate is
a. Cl^Θ
b. ClO₂^Θ
c. ClO₃^Θ
d. ClO^Θ
Answer:
b. ClO₂^Θ

Question viii.
The elementary reaction O₂(g) + O(g) → 2O₂(g) is
a. unimolecular and second order
b. bimolecular and first order
c. bimolecular and second order
d. unimolecular and first order
Answer:
c. bimolecular and second order

Question ix.
Rate law for the reaction, 2NO + Cl₂ → 2 NOCl is rate = k[NO₂]²[Cl₂]. Thus k would increase with
a. increase of temperature
b. increase of concentration of NO
c. increase of concentration of Cl₂
d. increase of concentrations of both Cl₂ and NO
Answer:
a. increase of temperature

Question x.
For an endothermic reaction, X ⇌ Y. If E f is activation energy of the forward reaction and Er that for reverse reaction, which of the following is correct?
a. E_f = E_r
b. E_f < E_r
c. E_f > E_r
d. ∆H = E_f – E_r is negative
Answer:
(c) Ef → Er

2. Answer the following in one or two sentences.

Question i.
For the reaction,
N₂(g) + 3 H₂(g) → 2NH₃(g), what is the relationship among \(\frac{\mathrm{d}\left[\mathrm{N}_{2}\right]}{\mathrm{dt}}\)\(\frac{\mathrm{d}\left[\mathrm{H}_{2}\right]}{\mathrm{dt}} \text { and } \frac{\mathrm{d}\left[\mathrm{NH}_{3}\right]}{\mathrm{dt}} ?\)
Answer:
N_2(g) + 3H_2(g) → 2NH_3(g)
From the above reaction, when 1 mole of N₂ reacts, 3 moles of H₂ are consumed and 2 moles of NH₃ are formed.

If the instantaneous rate R of the reaction is represented in terms of rate of the consumption of N₂ then, \(R=-\frac{d\left[\mathrm{~N}_{2}\right]}{d t}\)

Hence the rate of reaction in terms of concentration changes in N₂, H₂ and NH₃ may be represented as,

Question ii.
For the reaction,
CH₃Br(aq) + OH-(aq) → CH₃OH^Θ (aq) +Br^Θ (aq), rate law is rate = k[CH₃Br][OH^Θ]
a. How does reaction rate changes if [OH^Θ] is decreased by a factor of 5?
b. What is change in rate if concentrations of both reactants are doubled?
Solution :
Given :
(a) Rate = R = k [CH₃Br] x [OH^–]
If R₁ and R₂ are initial and final rates of reaction then,

Rate will be increased 4 time.

Question iii.
What is the relationship between coeffients of reactants in a balanced equation for an overall reaction and exponents in rate law. In what case the coeffients are the exponents?
Answer:
Explanation : Consider the following reaction, aA + bB → products

If the rate of the reaction depends on the concentrations of the reactants A and B, then, by rate law,
R α [A]^a [B]^b
∴ R = k [A]^a [B^b
where [A] = concentration of A and
[B] = concentration of B

The proportionality constant k is called the velocity constant, rate constant or specific rate of the reaction.

a and b are the exponents or the powers of the concentrations of the reactants A and B respectively when observed experimentally.

The exponents or powers may not be necessarily a and b but may be different x and y depending on experimental observations. Then the rate R will be,
R = k [A]^x [B]^y
For example, if x = 1 and y = 2, then,
R = k [A] x [B]²

Question iv.
Why all collisions between reactant molecules do not lead to a chemical reaction?
Answer:
(i) Collisions of reactant molecules : The basic re-quirements of a reaction is that the reacting species (atoms, ions or molecules) must come together and collide for a reaction to occur. Therefore the rate of the reaction shall depend on the rate and frequency of collisions which increase with the amount of reacting species and temperature.

However it is observed that the rate of reaction is very low as compared to the rate of collisions between reacting species in gaseous phase or liquid phase. This suggests that all the collisions are not fruitful leading to a reaction. Hence it is necessary to consider another factor like energy of colliding species along with collision frequency.

(ii) Energy requirement (Activation energy) : The colliding molecules must possess a certain mini-mum energy called activation energy required far breaking and making bonds resulting in the reaction. This implies that the colliding molecules must have energy equal to or greater than the activation energy. The colliding molecules with less energy do not react.

(iii) Orientation of reactant molecules : The concept of activation energy is satisfactory in case of simple molecules or ions but not in case of complex or higher polyatomic molecules. It is observed that the rates of reaction are less as compared to the rates of collisions between activated molecules with activation energy.

This suggests that in addition, the colliding molecules must have proper orientations relative to each other during collisions. For example, consider the reaction, A – B-l-C → A + B – C. For the reaction to occur, C must collide with B while collisions with A will not be fruitful. Since B has to bond with C.

Question v.
What is the activation energy of a reaction?
Answer:
Activation energy : The energy required to form activated complex or transition state from the reactant molecules is called activation energy.
OR
The height of energy barrier in the energy profile diagram is called activation energy.

Question vi.
What are the units for rate constants for zero order and second order reactions if time is expressed in seconds and concentration of reactants in mol/L?
Answer:
(a) For a zero order reaction, the rate constant has units, molL^-1s^-1.
(b) For second order reaction,
Rate = k x [Reactant]²

Question vii.
Write Arrhenius equation and explain the terms involved in it.
Answer:
Arrhenius equation is represented as k = A x e^-E_a/RT
where
k = Rate constant at absolute temperature T
E_a = Energy of activation R = Gas constant
A = Frequency factor or pre-exponential factor.

Question viii.
What is the rate determining step?
Answer:
Many chemical reactions take place in a series of elementary steps. Among many steps of the reaction, one of the steps is the slowest step compared to other steps.

Rate determining step : The slowest step in the reaction mechanism which involves many steps is called the rate-determining step.

Question ix.
Write the relationships between rate constant and half life of fist order and zeroth order reactions.
Answer:
(a) For first order reaction, half-life period t_1/2 is, \(t_{1 / 2}=\frac{0.693}{k}\) where k is the rate constant.
(b) For zeroth-order reaction, half half period (t_1/2) is, \(t_{1 / 2}=\frac{[\mathrm{A}]_{0}}{2 k}\) where k is the rate constant and [A]₀ is initial concentration of the reactant.

Question x.
How do half lives of the fist order and zero order reactions change with initial concentration of reactants?
Answer:
(A) For the first order reaction, half life, t_1/2 is given by, \(t_{1 / 2}=\frac{0.693}{k}\) where k is rate constant. Hence it is independent of initial concentration of the reactant.

(B) Zero order reaction,
\(t_{1 / 2}=\frac{[\mathrm{A}]_{0}}{2 k}\) where [A]₀ is initial concentration of the reactant.

Hence, half life period increases with the increase in concentration of the reactant.

3. Answer the following in brief.

Question i.
How instantaneous rate of reaction is determined?
Answer:
(1) The instantaneous rate is expressed as an infinite¬simal change in concentration (- dc) of the reactant with the infinitesimal change in time (dt).
For a reaction, A → B, let an infinitesimal change in A be – dc in time dt, then Rate \(=\frac{d[\mathrm{~A}]}{d t}\).

Hence, it is represented as,
∴ Instantaneous rate \(=-\frac{d[\mathrm{~A}]}{d t}\)

The negative sign indicates a decrease in the concentration of A.

It is obtained by drawing a tangent to the curve obtained by plotting the concentration against the time. Hence, the slope at a given point represents the instantaneous rate of the reaction.

(2) The instantaneous rate can also be expressed as an infinitesimal change (or increase) in the concentration of the product with the infinitesimal change in time (dt).

Let dB be an infinitesimal change in the concentration of product B in time dt, then Rate \(=\frac{d[\mathrm{~B}]}{d t}=\frac{d x}{d t}\).

Hence,
Instantaneous rate \(=\frac{d x}{d t}\)

It is obtained from the slope of the curve obtained by plotting the concentration of the product against time.

The instantaneous rate is more useful in obtaining the rate law integrated equations.

Question ii.
Distinguish between order and molecularity of a reaction.
Answer:

Question iii.
A reaction takes place in two steps,
1. NO(g) + Cl₂(g) NOCl₂(g)
2. NOCl₂(g) + NO(g) → 2NOCl(g)
a. Write the overall reaction.
b. Identify reaction intermediate.
c. What is the molecularity of each step?
Solution :
Given :
(1) NO_(g) + Cl_2(g) → NOCl_2(g)
(2) NOCl_2(g) + NO_(g) → 2NOCl_(g)

(a) Overall reaction is obtained by adding both the reactions
2NO_(g) + Cl_2(g) → 2NOCl_2(g)
(b) The reaction intermediate is NOCl₂, since it is formed in first step and consumed in the second step.
(c) Since the first step is a slow and rate determin­ing step, the molecularity is two.

Since the second step is a fast step its molecularity is not considered.

Question iv.
Obtain the relationship between the rate constant and half-life of a fist order reaction.
Answer:
Consider the following reaction,

If [A]₀ and [A]t are the concentrations of A at start and after time t, then [A]₀ = a and [A]_t = a – x.

The velocity constant or the specific rate constant k for the first order reaction can be represented as,

where, a is the initial concentration of the reactant A, x is the concentration of the product B after time t, so that (a – x) is the concentration of the reactant A after time t.

Half-life of a reaction : The time required to reduce the concentration of the reactant to half of its initial value is called the half-life period or the half-life of the reaction.

If t_1/2 is the half-life of a reaction, then at t = t_1/2, x = a/2, hence a – x = a – a/2 = a/2

Hence, for a first order reaction, the half-life of the reaction is independent of the initial concentration of the reactant.

Question v.
How will you represent zeroth-order reaction graphically?
Answer:
(1) A graph of concentration against time : In case of a zero-order reaction, the rate of reaction is independent of the concentration of the reactant. The concentration [A]_t of the reactant at a time t is given by
[A]_t = – kt + [A]₀ (y = – mx + c)
where [A]₀ is the initial concentration of the reactant and k is a rate constant.

Hence in case of zero order reaction, when the concentration of the reactant is plotted against time, a straight line with the slope equal to – k is obtained. The concentration of the reactants de-crease with time. The intercept on the concentration axis gives the initial concentration, [A]₀.

(2) A graph of rate of a reaction against the concen-tration of the reactant: Rate of a zero order reaction is independent of the concentration of the reactant.

Rate, R = k [A]⁰ = k

Hence even if the concentration of the reactant decreases, the rate of the reaction remains constant.

Therefore if the rate of a zero order reaction is plotted against concentration, then a straight line with zero slope is obtained indicating, no change in the rate of the reaction with a change in the concentration of the reactants.

(3) A graph of half-life period against concentration : The half-life period of a zero-order reaction is given by, \(t_{1 / 2}=\frac{[\mathrm{A}]_{0}}{2 k}\) where [A]₀ is initial con-centration of the reactant and k is the rate constant. Hence the half-life period is directly proportional to the concentration.

When a graph of t_1/2 is plotted against concentration, a straight line passing through origin is obtained, and the slope gives \(\frac{1}{2 k}\), where k is the rate constant.

Question vi.
What are pseudo-fist order reactions? Give one example and explain why it is pseudo-fist order.
Answer:
Pseudo-first-order reaction : A reaction which has higher-order true rate law but is experimentally found to behave as first order is called pseudo first order reaction.
Explanation : Consider an acid hydrolysis reaction of an ester like methyl acetate.
CH₃COOCH_3(aq) + H₂O₍₁₎ \(\stackrel{\mathrm{H}_{(\mathrm{aq})}^{+}}{\longrightarrow}\) CH₃COOH_(aq) + CH₃OH_(aq)
Since the reaction involves two substances, ester and water, it is a bimolecular reaction and the true rate law should be, Rate = k’ [CH₃COOCH₃] x [H₂O]

Hence the reaction is expected to follow second order kinetics. However experimentally it is found that the reaction follows first order kinetics.

This is because solvent water being in a large excess, its concentration remains constant. Hence, [H₂O] = constant = k”
Rate = k [CH₃COOCH₃] x [H₂O]
= k [CH₃COOCH₃] x k”
= k’ x k” x [CH₃COOCH₃]
If k’ x k” = k, then Rate = k [CH₃COOCH₃],

This indicates that second-order true rate law is forced into first order rate law. Therefore this bimolecular reaction which appears of second order is called pseudo first order reaction.

Question vii.
What are the requirements for the colliding reactant molecules to lead to products?
Answer:
Collisions of reactant molecules : The basic re­quirements of a reaction is that the reacting species (atoms, ions or molecules) must come together and collide for a reaction to occur. Therefore the rate of the reaction shall depend on the rate and frequency of collisions which increase with the amount of reacting species and temperature.

However it is observed that the rate of reaction is very low as compared to the rate of collisions between reacting species in gaseous phase or liquid phase. This suggests that all the collisions are not fruitful leading to a reaction. Hence it is necessary to consider another factor like energy of colliding species along with collision frequency.

Energy requirement (Activation energy) : The colliding molecules must possess a certain mini­mum energy called activation energy required far breaking and making bonds resulting in the reac­tion. This implies that the colliding molecules must have energy equal to or greater than the activation energy. The colliding molecules with less energy do not react.

Orientation of reactant molecules : The concept of activation energy is satisfactory in case of simple molecules or ions but not in case of complex or higher polyatomic molecules. It is observed that the rates of reaction are less as compared to the rates of collisions between activated molecules with activa­tion energy.

This suggests that in addition, the colliding mole­cules must have proper orientations relative to each other during collisions. For example, consider the reaction, A – B + C → A + B – C. For the reaction to occur, C must collide with B while collisions with A will not be fruitful. Since B has to bond with C.

Question viii.
How catalyst increases the rate of reaction? Explain with the help of a potential energy diagram for catalyzed and uncatalyzed reactions.
Answer:
(i) A catalyst is a substance, when added to the reactants, increases the rate of the reaction without being consumed. For example, the decomposition of KClO₃ in the presence of small amount of MnO₂ is very fast but very slow in the absence of MnO₂.

2KClO_3(s) \(\frac{\mathrm{MnO}_{2}}{\Delta}\) 2KCl_(s) + 3O_2(g)

(ii) The phenomenon of catalysed reaction is called catalysis and depends on nature of the catalyst. In heterogeneous catalysis, the reactant molecules are adsorbed on the solid catalyst surface while in case of homogeneous catalysis, the catalyst reacts with one of the reactants, forms intermediate and decomposes reforming original catalyst and the products.

(iii) The catalyst provides alternative and lower energy path or mechanism for the reaction.

(iv) In the presence of the catalyst, the activation energy of the reaction is lowered. The height of activation energy barrier is less than that in the uncatalysed reaction.

(v) Due to lowering of energy of activation, (E_a) the number of molecules possessing E_a increases, hence the rate of the reaction increases.

(vi) The rate constant = k = A x e^-E_a/RT where A is a frequency factor and hence the rates of the catalysed reaction are higher than those of un-catalysed reactions.

(vii) The catalyst does not change the extent of the reaction but hastens the reaction.

(viii) The catalyst enters the reaction but does not appear in the balanced equation since it is consumed in one step and regenerated in the another.

Question ix.
Explain with the help of the Arrhenius equation, how does the rate of reaction changes with (a) temperature and (b) activation energy.
Answer:
(a) By Arrhenius equation, k = Ax e^-E_a/RT where k is rate constant, A is a frequency factor and Ed is energy of activation at temperature T. As E_a increases, the rate constant and rate of the reaction decreases.

(b) As temperature increases E_a/RT decreases but due to negative sign, k and rate increase with the increase in temperature.

Question x.
Derive the integrated rate law for first order reaction.
Answer:
Consider following gas phase reaction,

Let initial pressure of A be P₀ at t = 0. If after time t the pressure of a A decreases by jc then the partial pressures of the substances will be, P_A = P_Q – x; P_B = x and P_c = x

Total pressure will be,

P_T + P₀ – x + x + x = Po + x
∴ x = P_T – P_n

The partial pressures at time t will be,

Question xi.
How will you represent first-order reactions graphically.
Answer:
(1) A graph of rate of a reaction and concentra­tion : The differential rate law for first-order reac­tion, A → Products is represented as, Rate = [/latex]-\frac{d[\mathrm{~A}]}{d t}=k[\mathrm{~A}]\(

∴ Rate = k x [A]_t (y = mx). When the rate of a first order reaction is plotted against concentration, [A]_t, a straight line graph is obtained.

With the increase in the concentration [A]_t, rate R, increases. The slope of the line gives the value of rate constant k.

(2) A graph of concentration against time : When the concentration of the reactant is plotted against time t, a curve is obtained. The concentration [A], of the reactant decreases exponentially with time. The variation in the concentration can be represented as,

where [A]₀ and [A]_t are initial and final concentra­tions the reactant and k is the rate constant. The time required to complete the first order reaction is infinity.

(3) A graph of log₁₀ (a – x) against time t :

When log₁₀(a – x) is plotted against time t, a straight line with negative slope is obtained, from which the velocity constant k can be calculated.

(4) A graph of half-life period and concentration : The half-life period, t_1/2 of a first order reaction is given by, where k is the rate constant.

For the given reaction at a constant temperature, t_1/2 is constant and independent of the concentration of the reactant.

Hence when a graph of t_1/2 is plotted against concentration, a straight line parallel to the concen­tration axis (slope = zero) is obtained.

(5) A graph of log₁₀ [latex]\left(\frac{a}{a-x}\right)\) against time : The rate constant, for a first order reaction is represented as, where [A₀] and [A]_t are the respective initial and final concentrations of the reactant after time t.


When \(\log _{10}\left(\frac{a}{a-x}\right)\) is plotted against time t, a straight line graph passing through the origin is obtained and the slope gives the value of k/2.303. From this slope, the rate constant can be calculated.

Question xii.
Derive the integrated rate law for the first order reaction, A(g) → B(g) + C(g) in terms of pressure.
Answer:
Consider following gas phase reaction,

Let initial pressure of A be P₀ at t = 0. If after time t the pressure of a A decreases by jc then the partial pressures of the substances will be, P_A = P_Q – x; P_B = x and P_c = x

Total pressure will be,

P_T + P₀ – x + x + x = Po + x
∴ x = P_T – P_n

The partial pressures at time t will be,

Question xiii.
What is zeroth-order reaction? Derive its integrated rate law. What are the units of rate constant?
Answer:
Definition : Zero order reaction : A reaction in which the rate of the reaction does not depend on the concentration of any reactant taking part in the reaction is called zero order reaction.

Consider a zero order reaction, A → Products
The rate of the reaction is, Rate \(=\frac{-d[\mathrm{~A}]}{d t}\)

By rate law,
Rate = k x [A]⁰ = k
∴ – d[A] = k x dt

If [A]₀ is the initial concentration of the reactant A at t = 0 and [A]_t is the concentration of A present after time t, then by integrating above equation,

This is the integrated rate law expression for rate constant for zero order reaction.
∴ k x t = [A]₀ – [A]_t
∴ [A]_t = – kt + A₀

For a zero order reaction :
The rate of reaction is R = k [A]⁰ = k
Hence, the velocity constant k has the unit of the rate of the reaction, i.e., mol dm^-3 s^-1.

Question xiv.
How will you determine activation energy: (a) graphically using Arrhenius equation (b) from rate constants at two different temperatures?
Answer:
(a) By Arrhenius equation,
Rate constant = = A x e^-E_a/RT where A is a fre-quency factor.

When log₁₀k is plotted against 1/T a straight line with negative slope is obtained. From the slope of the graph, energy of activation E_a, is obtained as follows :
Slope = \(\frac{E_{\mathrm{a}}}{2.303 R}\)
∴ Ea = 2303R x sloPe

(b) For the given reaction, rate constants k₁ and k₂ are measured at two different temperatures T₁ and T₂ respectively. Then \(\log _{10} \frac{k_{2}}{k_{1}}=\frac{E_{\mathrm{a}}\left(T_{2}-T_{1}\right)}{2.303 R \times T_{1} \times T_{2}}\) where E_a is the energy of activation.

Hence by substituting appropriate values, energy of activation E_a for the reaction is determined.

Question xv.
Explain graphically the effect of temperature on the rate of reaction.
Answer:
(i) It has been observed that the rates of chemical reactions increase with the increase in temperature.
(ii) The kinetic energy of the molecules increases with the increase in temperature. The fraction of molecules possessing minimum energy barrier,
i. e. activation energy E_a increases with increase in temperature.
(iii) Hence the fraction of colliding molecules that possess kinetic energy (E_a) also increases, hence the rate of the reaction increases with increase in temperature.

(iv) The above figure shows that the area that represents the fraction of molecules with kinetic energy exceeding E_a is greater at higher temperature T₂ than at lower temperature T₁. This explains that the rate of the reaction increases at higher temperature.
(v) The shaded area to the right of activation energy E_a represents fraction of collisions of activated molecules having energy E_a or greater.

Question xvi.
Explain graphically the effect of catalyst on the rate of reaction.
Answer:
(i) The phenomenon of catalysed reaction is called catalysis and depends on nature of the catalyst. In heterogeneous catalysis, the reactant molecules are adsorbed on the solid catalyst surface while in case of homogeneous catalysis, the catalyst reacts with one of the reactants, forms intermediate and decomposes reforming original catalyst and the products.
(ii) The catalyst provides alternative and lower energy path or mechanism for the reaction.
(iii) In the presence of the catalyst, the activation energy of the reaction is lowered. The height of activation energy barrier is less than that in the uncatalysed reaction.

Question xvii.
For the reaction 2A + B → products, find the rate law from the following data.

Solution :
Given : 2A + B → Products
Rates : R₁ = 0.15 Ms^-1 R₂ = 0.3 Ms^-1
[A]₁ = 0.3 M [A]₂ = 0.6 M
[B]₁ = 0.05 M [B]₂ = 0.05 M
(i) If order of the reaction in A is x and in B is y then, by rate law,

∴ y = 1. Hence the reaction has order one in B.
The order of overall reaction = n = n_A + n_B = 1 + 1 = 2

Answer:
(i) Rate law : Rate = fc [A] x [B]
Rate constant = k = 10M^-1s^-1
Order of the reaction = 2

4. Solve

Question i.
In a first order reaction, the concentration of reactant decreases from 20 mmol dm^-3 to 8 mmol dm^-3 in 38 minutes. What is the half life of reaction? (28.7 min)
Solution :
Given: [A]₀ =20 mmol dm^-3;
[A]_t=8 mmol dm^-3; t=38 mm;

Answer:
Half life period = 28.74 min

Question ii.
The half life of a first order reaction is 1.7 hours. How long will it take for 20% of the reactant to react? (32.9 min)
Solution :
Given : t_1/2 = 1.7 hr; [A]₀ = 100;
[A]_t = 100 – 20 = 80; t =?
\(t_{1 / 2}=\frac{0.693}{k}\)

Answer:
Time required = t = 32.86 min

Question iii.
The energy of activation for a first order reaction is 104 kJ/mol. The rate constant at 25 0C is 3.7 × 10^-5 s^-1. What is the rate constant at 30⁰C? (R = 8.314 J/K mol) (7.4 × 10^-5)
Solution :

Answer:
k₂ = 7.382 x 10^-5 s^-1

Question iv.
What is the energy of activation of a reaction whose rate constant doubles when the temperature changes from 303 K to 313 K? (54.66 kJ/mol)
Solution :
Given : k₂ = 2k_t, T₁ = 303 K; T₂ = 313 K; E_a = ?

Answer:
Energy of activation = E_a = 54.66 kJ

Question v.
The rate constant of a reaction at 5000C is 1.6 × 10³ M^-1 s^-1. What is the frequency factor of the reaction if its activation energy is 56 kJ/mol. (9.72 × 106 M^-1 s^-1)
Solution :

Answer:
Frequency factor = A = 9.727 x 10⁶ M^-1s^-1

Question vi.
Show that time required for 99.9% completion of a first order reaction is three times the time required for 90% completion.
Solution :
Given : For 99.9 % completion, if [A]₀ = 100,

If t₁ and t₂ are the times required for 99.9 % and 90 % completion of reaction respectively, then

Answer:
Time required for 99.9 % completion of a first order reaction is three time the time required for 90 % completion of the reaction.

Question vii.
A first order reaction takes 40 minutes for 30% decomposition. Calculate its half life. (77.66 min)
Solution :

Answer:
Half life period = 77.70 min.

Question viii.
The rate constant for the first order reaction is given by log₁₀ k = 14.34 – 1.25 × 10⁴ T. Calculate activation energy of the reaction. (239.3 kJ/mol)
Solution :
Given : log₁₀ k = 14.34 – \(\frac{1.25 \times 10^{4}}{T}\) ……………………. (1)
From Arrhenius equation we can write,
\(\log _{10} k=\log _{10} A-\frac{E_{\mathrm{a}}}{2.303 R \times T}\) ……………………. (2)
By comparing equations (1) and (2),
\(\frac{E_{\mathrm{a}}}{2.303 \times R}\) = 1.25 x 10⁴
∴ Ea = 1.25 x 10⁴ x 2.303 x R
= 1.25 x 10⁴ x 2.303 x 8.314
= 23.93 x 10⁴ = 239.3 kJ mol^-1

[Note : Frequency factor A may also be calculated as follows : log₁₀ A = 14.34
∴ A = Antilog 14.34 = 2.188 x 10⁴
Answer:
Energy of activation = E_a = 239.3 kJ mol^-1.

Question ix.
What fraction of molecules in a gas at 300 K collide with an energy equal to activation energy of 50 kJ/mol? (2 × 10^-9)
Solution :
Given : T = 300 K; E_a = 50 kJ mol^-1
= 50 x 10³ mol^-1
The fraction of molecules undergoing fruitful collisions is

Answer:
Fraction of molecules undergoing collision = 2 x 10^-9

Activity :
1. If you wish to determine the reaction order and rate constant for the reaction, 2AB₂ → A₂ + 2B₂.
a) What data would you collect?
b) How would you use these data to determine whether the reaction is zeroth or first order?

2. The activation energy for two reactions are E_a and E’_a with E_a > E’_a. If the temperature of reacting system increases from T₁ to T₂, predict which of the following is correct?

k values are rate constants at lower temperatures and k values at higher temperatures.

12th Chemistry Digest Chapter 6 Chemical Kinetics Intext Questions and Answers

(Textbook Page No 121)

Question 1.
Write the expressions for rates of reaction for :
2N₂O_5(g) → 4NO_2(g) + O_2(g)?
Answer:
For the given reaction, Rate of reaction =
\(=R=-\frac{1}{2} \frac{d\left[\mathrm{~N}_{2} \mathrm{O}_{5}\right]}{d t}\)
\(\begin{aligned}
&=+\frac{1}{4} \frac{d\left[\mathrm{NO}_{2}\right]}{d t} \\
&=+\frac{d\left[\mathrm{O}_{2}\right]}{d t}
\end{aligned}\)

Problem 6.1: (Textbook Page No 121)

Question 1.
For the reaction,
\(\mathbf{3 I}_{(a q)}^{-}+\mathbf{S}_{2} \mathbf{O}_{8(a q)}^{2-} \longrightarrow \mathbf{I}_{3(\text { (aq) }}^{-}+2 \mathbf{S O}_{4(\mathrm{aq})}^{2-}\)
Calculate (a) the rate of formation of I₃^–,
(b) the rates of consumption of 1 and S₂O and (c) the overall rate of reaction if the rate of formation of \(\mathrm{SO}_{4}^{2-}\) is 0.O22 moles dm^-3 sec^-1.
Answer:


∴ (a) Rate of formation of \(\mathrm{I}_{3}^{-}\) = 0.011 mol dm^-3 s^-1
(b) Rate of consumption of I^– = 0.033 mol dm^-3 s^-1
(c) Rate of consumption of \(\mathrm{S}_{2} \mathrm{O}_{8}^{2-}\) = 0.011 mol dm^-3 s^-1
(d) Overall rate of reaction = Rate of consumption of reactant = Rate of formation of product

Try this….. (Textbook Page No 122)

Question 1.
For the reaction :
NO_2(g) + CO_(g) → NO_(g) + CO_2(g), the rate of reaction is experimentally found to be proportional to the square of the concentration of NO2 and independent that of CO. Write the rate law.
Answer:
Since the rate of the reaction is proportional to [NO₂]² and [CO]⁰, the rate law is R = k[NO₂]² x [CO]⁰
∴ R = k[NO₂]².

Try this….. (Textbook Page No 124)

Question 1.
The reaction,
CHCl_3(g) + Cl_2(g) → CCl_4(g) + HCl_(g) is first order in CHCl₃ and 1/2 order in Cl₂. Write the rate law and overall order of reaction.
Answer:
Since the reaction is first order in CHCl₃ and 1/2 order in Cl₂, the rate law for the reaction will be, Rate = k[CHCl₃] X [Cl₂]^1/2
The overall order (n) of the reaction will be, n = l + = \(\frac{1}{2}=\frac{3}{2}\)

Use your brain power! (Textbook Page No 124)

Question 1.
The rate of the reaction 2A + B → 2C + D is 6 x 10^-4 mol dm^-3 s^-1 when [A] =[B] = O.3 mol dm^-3 If the reaction is of first order in A and zeroth order in B, what is the rate constant?
Answer:
For the reaction,
2A + B → 2C + D,

(Problem 6.7) (Textbook Page No 126)

Question 1.
A reaction occurs in the following steps :
(i) NO_2(g) + F_2(g) → NO₂F_(g) + F_(g) (slow)
(ii) F_(g) + NO_2(g) → NO₂F_(g) (fast)
(a) Write the equation of overall reaction.
(b) Write down rate law.
(c) Identify the reaction intermediate.
Solution :
(a) The addition of two steps gives the overall reaction as
2NO_2(g) + F_2(g) → 2NO₂ F_(g)
(b) Step (i) is slow. The rate law of the reaction is predicted from its stoichiometry. Thus, rate = k [NO₂] [F₂]
(c) F is produced in step (i) and consumed in step (ii) hence F is the reaction intermediate.

Try this….. (Textbook Page No 126)

Question 1.
A complex reaction takes place in two steps :
(i) NO_(g) + O_3(g) → NO_3(g) + O_(g)
(ii) NO_3(g) + O_(g) → NO_2(g) + O_2(g)
The predicted rate law is rate = k [NO] [O₃]. Identify the rate-determining step. Write the overall reaction. Which is the reaction inter-mediate? Why?
Answer:
(i) NO_(g) + O_3(g) → NO_3(g) + O_(g)
(ii) NO_3(g) + O_(g) → NO_2(g) + O_2(g)
(a) The first step is slow and rate determining step since the rate depends on concentrations of NO_(g) and O_3(g). (Given : Rate = k [NO] x [O])
(b) The overall reaction is the combination of two steps.
NO_(g) ⁺ O_3(g) → NO_2(g) + O_2(g)
(c) NO_3(g) and O_(g) are reaction intermediates. They are formed in first step (i) and removed in the second step (ii).

Try this….. (Textbook Page No 129)

Question 1.
The half-life of a first-order reaction is 0.5 min. Calculate (a) time needed for the reactant to reduce to 20% and (b) the amount decomposed in 55 s.
Answer:

Try this….. (Textbook Page No 123)

Question 1.
For the reaction 2A + 2B → 2C + D, if concentration of A is doubled at constant [B] the rate increases by a factor of 4. If the concentration of B is doubled with [A] being constant the rate is doubled. Write the rate law of the reaction.
Answer:
Rate = R₁ = k[A]^x [B]^y
When concentration of A = [2A] and

Hence order with respect to A is 2 and with respect to B is 1. By rate law,
Rate = A: [A]² [B]

Question 2.
The rate law for the reaction A + B → C is found to be rate = k [A]² x [B]. The rate constant of the reaction at 25 °C is 6.25 M^-2 S^-1. What is the rate of reaction when [A] = 1.0 mol dm^-3 and [B] = 0.2 mol dm^-3?
Answer:
Rate = k x [A]² x [B]
= 6.25 x 1² x 0.2
Rate = 1.25 x 10² mol dm^-3 s^-1

Maharashtra State Board 12th Std Chemistry Textbook Solutions

• Solid State Class 12 Chemistry Textbook Solutions
• Solutions Class 12 Chemistry Textbook Solutions
• Ionic Equilibria Class 12 Chemistry Textbook Solutions
• Chemical Thermodynamics Class 12 Chemistry Textbook Solutions
• Electrochemistry Class 12 Chemistry Textbook Solutions
• Chemical Kinetics Class 12 Chemistry Textbook Solutions
• Elements of Groups 16, 17 and 18 Class 12 Chemistry Textbook Solutions
• Transition and Inner Transition Elements Class 12 Chemistry Textbook Solutions

Electrochemistry Class 12 Exercise Question Answers Solutions Maharashtra Board

Balbharti Maharashtra State Board 12th Chemistry Textbook Solutions Chapter 5 Electrochemistry Textbook Exercise Questions and Answers.

Class 12 Chemistry Chapter 5 Exercise Solutions Maharashtra Board

Chemistry Class 12 Chapter 5 Exercise Solutions

1. Choose the most correct option.

Question i.
Two solutions have the ratio of their concentrations 0.4 and ratio of their conductivities 0.216. The ratio of their molar conductivities will be
(a) 0.54
(b) 11.574
(c) 0.0864
(d) 1.852
Answer:
(a) 0.54

Question ii.
On diluting the solution of an electrolyte,
(a) both ∧ and κ increase
(b) both ∧ and κ decrease
(c) ∧ increases and κ decreases
(d) ∧ decreases and κ increases
Answer:
(c) ∧ increases and κ decreases

Question iii.
1 S m² mol^-1 is equal to
(a) 10^-4 S m² mol^-1
(b) 10⁴ Ω^-1 cm² mol^-1
(c) 10^-2 S cm² mol^-1
(d) 10² Ω^-1 cm² mol^-1
Answer:
(b) 10⁴Ω^-1 cm² mol^-1

Question iv.
The standard potential of the cell in which the following reaction occurs
H₂₊ (g, 1 atm) + Cu²⁺ (1 M) → 2H (1 M) + Cu_(s), (\(E_{\mathrm{Cu}}^{0}\) = 0.34 V) is
(a) – 0.34 V
(b) 0.34 V
(c) 0.17 V
(d) -0.17 V
Answer:
(b) 0.34 V

Question v.
For the cell, Pb_(s)|Pb²⁺ (1 M)|| Ag⁺ (1 M)|Ag_(s), if concentration of an ion in the anode compartment is increased by a factor of 10, the emf of the cell will
(a) increase by 10 V
(b) increase by 0.0296 V
(c) decrease by 10 V
(d) decrease by 0.0296 V
Answer:
(d) decrease by 0.0296 V

Question vi.
Consider the half reactions with standard potentials

The strongest oxidising and reducing agents respectively are
(a) Ag and Fe²⁺
(b) Ag⁺ and Fe
(c) Pb²⁺ and I^–
(d) I₂ and Fe²⁺
Answer:
(b) Ag⁺ and Fe

Question vii.
For the reaction
Ni_(s) + Cu²⁺ (1 M) → Ni²⁺ (1 M) + Cu_(s), \(E_{\text {cell }}^{0}\) = 0.57 V. Hence ΔG⁰ of the reaction is
(a) 110 kJ
(b) -110 kJ
(c) 55 kJ
(d) -55 kJ
Answer:
(b) -110 kJ

Question viii.
Which of the following is not correct ?
(a) Gibbs energy is an extensive property
(b) Electrode potential or cell potential is an intensive property.
(c) Electrical work = -ΔG
(d) If half reaction is multiplied by a numerical factor, the corresponding E⁰ value is also multiplied by the same factor.
Answer:
(d) If half reaction is multiplied by a numerical factor, the corresponding E⁰ value is also multiplied by the same factor.

Question ix.
The oxidation reaction that takes place in lead storage battery during discharge is

Answer:
(c) \(\mathrm{Pb}_{(\mathrm{s})}+\mathrm{SO}_{4(\mathrm{aq})}{ }^{2-} \longrightarrow \mathrm{PbSO}_{4(\mathrm{~s})}+2 \mathrm{e}^{-}\)

Question x.
Which of the following expressions represent molar conductivity of Al₂(SO₄)₃ ?

Answer:
(b) \(2 \lambda_{\mathrm{Al}^{3+}}^{0}+3 \lambda_{\mathrm{SO}_{4}^{2-}}^{0}\)

2. Answer the following in one or two sentences.

Question i.
What is a cell constant ?
Answer:
(A) Cell constant of a conductivity cell is defined as the ratio of the distance between the electrodes divided by the area of cross section of the electrodes.

In SI units it is expressed as m-1.

Question ii.
Write the relationship between conductivity and molar conductivity and hence unit of molar conductivity.
Answer:
If k is conductivity and ∧_m is molar conductivity then, ∧_m = \(\frac{\kappa \times 1000}{C}\)
Unit of molar conductivity is, Ω^-1 cm² mol^-1 or S cm² mol^-1.

Question iii.
Write the electrode reactions during electrolysis of molten KCl.
Answer:

Question iv.
Write any two functions of salt bridge.
Answer:
The functions of a salt bridge are :

• It maintains the electrical contact between the two electrode solutions of the half cells.
• It prevents the mixing of electrode solutions.
• It maintains the electrical neutrality in both the solutions of two half cells by a flow of ions.
• It eliminates the liquid junction potential.

Question v.
What is standard cell potential for the reaction
3Ni_(s) + 2Al³⁺ (1M) → 3NI²⁺ (1M) + 2Al_(s)
if \(\boldsymbol{E}_{\mathrm{Ni}}^{0}\) = – 0.25 V and \(\boldsymbol{E}_{\mathrm{Al}}^{0}\) = -1.66V?
Solution :
Given : E⁰_Ni²⁺/Ni = -0.25 V
E⁰_Al³⁺/Al = – 1.66 V; E⁰_cell = ?
Since Ni is oxidised and Al³⁺ is reduced,
\(E_{\text {cell }}^{0}=E_{\mathrm{Al}^{3+} / \mathrm{Al}}^{0}-E_{\mathrm{Ni}^{2+} / \mathrm{Ni}}^{0}\)
= – 1.66 – (-0.25)
= – 1.41 V
Ans. \(E_{\text {cell }}^{0}\) = -1.41 V
[Note : Since \(E_{\text {cell }}^{0}\) is negative, the given reaction is not possible but reverse reaction is possible.]

Question vi.
Write Nerst equation. What part of it represents the correction factor for nonstandard state conditions ?
Answer:
(1) Nernst equation for cell potential is,

(2) The part of equation namely,

represents the correction factor for nonstandard state conditions.

Question vii.
Under what conditions the cell potential is called standard cell potential ?
Answer:
In the standard cell, the active masses of the substances taking part in the electrochemical reaction have unit value, i.e., 1 M solution or ions and 1 atm gas.

Question viii.
Formulate a cell from the following electrode reactions :
\(\mathbf{A u}_{(\mathrm{aq})}^{3+}+\mathbf{3 e}^{-} \longrightarrow \mathbf{A} \mathbf{u}_{(\mathrm{s})}\)
\(\mathbf{M g}_{(\mathbf{s})} \longrightarrow \mathbf{M g}_{(\mathrm{aq})}^{2+}+\mathbf{2 e}^{-}\)
Answer:
An electrochemical cell from above electrode reactions is,

Question ix.
How many electrons would have a total charge of 1 coulomb ?
Answer:
Given : 1 Faraday = charge on 1 mol of electrons
= 6.022 × 10²³ electrons and 1 Faraday = 96500 C
∵ 96500 C = 6.022 × 10²³ electrons 6 022 × 10²³
∴ 1 C ≡ \(\frac{6.022 \times 10^{23}}{96500}\) = 6.24 × 10¹⁸ electrons
Ans. Number of electrons = 6.24 × 10¹⁸

Question x.
What is the significance of the single vertical line and double vertical line in the formulation galvanic cell.
Answer:
(i) Consider representation of Daniell cell,

Single vertical line represents separation of two phases, solid Zn_(s) and solution of ions.
(ii) Double vertical lines represent a salt bridge.

3. Answer the following in brief

Question i.
Explain the effect of dilution of solution on conductivity ?
Answer:

• The conductance of a solution is due to the presence of ions in the solution. More the ions, higher is the conductance of the solution.
• Conductivity or the specific conductance is the conductance of unit volume (1 cm³) of the electrolytic solution.
• The conductivity of the electrolytic solution always decreases with the decrease in the concentration of the electrolyte or the increase in dilution of the solution.
• On dilution, the concentration of the solution decreases, hence the number of (current carrying) ions per unit volume decreases. Therefore the conductivity of the solution decreases, with the decrease concentration or increase in dilution. (It is to be noted here that, molar conductivity increases with dilution.)

Question ii.
What is a salt bridge ?
Answer:
A salt bridge is a U-shaped glass tube containing a saturated solution of a strong electrolyte, like KCl, NH₄NO₃, Na₂SO₄ in a solidified agar-agar gel. A hot saturated solution of these electrolytes in 5% agar solution is filled in the U-shaped tube and allowed it to cool and solidify forming a gel.

Fig. 5.9 : Salt bridge
It is used to connect two half cells or electrodes forming a galvanic or voltaic cell.

Question iii.
Write electrode reactions for the electrolysis of aqueous NaCl.
Answer:
Reactions in electrolytic cell :
(i) Reduction half reaction at cathode : There are Na⁺ and H⁺ions but since H⁺ are more reducible than Na⁺, they undergo reduction liberating hydrogen and Na⁺ are left in the solution.
2H₂O_(l) + 2e^– → H_2(g) + 2OH^–_(aq) (reduction) E⁰ = -0.83 V

(ii) Oxidation half reaction at anode : At anode there are Cl^– and OH^–. But Cl^– ions are preferably oxidised due to less decomposition potential.

Net cell reaction : Since two electrons are gained at cathode and two electrons are released at anode for each redox step, the electrical neutrality is maintained. Hence we can write,

Since Na⁺ and OH^– are left in the solution, they form NaOH_(aq).

Question iv.
How many moles of electrons are passed when 0.8 ampere current is passed for 1 hour through molten CaCl₂ ?
Answer:
Given : I = 0.8 A; t = 1 × 60 × 60 = 3600 s
Number of moles of electrons = ?
Q = I × t
= 0.8 × 3600
= 2880 C
1 Faraday = 1 mol electrons
1 Faraday = 96500 C
∵ 96500 C = 1 mol electrons
∴ 2880 C ≡ \(\frac{2880}{96500}\)
= 0.02984 mol electrons
Ans. Number of moles of electrons = 0.02984

Question v.
Construct a galvanic cell from the electrodes Co³⁺|Co and Mn²⁺|Mn. \(\boldsymbol{E}_{\mathrm{Co}}^{0}\) = 1.82 V,
\(\boldsymbol{E}_{\mathrm{Mn}}^{0}\) = – 1.18V. Calculate \(\boldsymbol{E}_{\text {cell }}^{0}\).
Answer:

Question vi.
Using the relationsip between ∆G⁰ of cell reaction and the standard potential associated with it, how will you show that the electrical potential is an intensive property ?
Answer:
(1) For an electrochemical cell involving n number of electrons in the overall cell reaction,
ΔG⁰ = -nF\(E_{\text {cell }}^{0}\)
where ΔG⁰ is standard Gibbs energy change and \(E_{\text {cell }}^{0}\) is a standard cell potential.
(2) ∴ \(E_{\mathrm{cell}}^{0}=\frac{-\Delta G^{0}}{n F}\)
Since ΔG⁰ changes according to number of moles of electrons involved in the cell reaction, the ratio, ΔG⁰/nF remains constant.
(3) Therefore \(E_{\text {cell }}^{0}\) is independent of the amount of substance and it represents the intensive property.

Question vii.
Derive the relationship between standard cell potential and equilibrium constant of cell reaction.
Answer:
For any galvanic cell, the overall cell reaction at equilibrium can be represented as,
Reactants ⇌ Products.
[For example for Daniell cell,
\(\mathrm{Zn}_{(s)}+\mathrm{Cu}_{(\mathrm{aq})}^{2+} \rightleftharpoons \mathrm{Zn}_{(\mathrm{aq})}^{2+}+\mathrm{Cu}_{(\mathrm{s})}\) ]
The equilibrium constant, K for the reversible reaction will be, \(K=\frac{[\text { Products }]}{[\text { Reactants }]}\)

The equilibrium constant is related to the stan-dard free energy change Δ G⁰, as follows,
ΔG⁰ = -RTlnK
If \(E_{\text {cell }}^{0}\) is the standard cell potential (or emf) of the galvanic cell, then ΔG⁰ = -nFE⁰_cell
By comparing above equations,

Question viii.
It is impossible to measure the potential of a single electrode. Comment.
Answer:
(1)

Fig 5.12(a) : Measurement of single electrode potential

Fig 5.12(b) : Measurement of cell potential
According to Nemst theory, electrode potential is the potential difference between the metal and ionic layer around it at equilibrium, i.e. the potential across the electric double layer.

(2) For measuring the single electrode potential, one part of the double layer, that is metallic layer can be connected to the potentiometer but not the ionic layer. Hence, single electrode potential can’t be measured experimentally.

(3) When an electrochemical cell is developed by combining two half cells or electrodes, they can be connected to the potentiometer and the potential difference or cell potential can be measured.
E_cell = E₂ – E₁
where E₁ and E₂ are reduction potentials of two electrodes.

Question ix.
Why do the cell potential of lead accumulators decrease when it generates electricity ? How the cell potential can be increased ?
Answer:
Working of a lead accumulator :
(1) Discharging : When the electric current is withdrawn from lead accumulator, the following reactions take place :

(2) Net cell reaction :
(i) Thus, the overall cell reaction during discharging is

OR
Pb_(s) + PbO_2(s) + 2H₂SO_4(aq) → 2PbSO_4(s) + 2H₂O_(l)
The cell potential or emf of the cell depends upon the concentration of sulphuric acid. During the operation, the acid is consumed and its concentration decreases and specific gravity decreases from 1.28 to 1.17. As a result, the emf of the cell decreases. The emf of a fully charged cell is about 2.0 V.

(ii) Recharging of the cell : When the discharged battery is connected to external electric source and a higher external potential is applied the cell reaction gets reversed generating H₂SO₄.
Reduction at the -ve electrode or cathode :
PbSO4_(s) + 2e^– → Pb_(s) + \(\mathrm{SO}_{4(\mathrm{aq})}^{2-}\)
Oxidation at the + ve electrode or anode :

The emf of the accumulator depends only on the concentration of H₂SO₄.

Question x.
Write the electrode reactions and net cell reaction in NICAD battery.
Answer:
Reactions in the cell :
(i) Oxidation at cadmium anode :
Cd_(s) + 2OH^–_(aq) → Cd(OH)_2(s) + 2e^–
(ii) Reduction at NiO_2(s) cathode :
NiO_2(s) + 2H₂O_(l) + 2e^– → Ni(OH)_2(s) + 2OH^–_(aq)
The overall cell reaction is the combination of above two reactions.
Cd_(s) + NiO_2(s) + 2H₂O_(l) → Cd(OH)_2(s) + Ni(OH)_2(s)

4. Answer the following :

Question i.
What is Kohrausch law of independent migration of ions? How is it useful in obtaining molar conductivity at zero concentration of a weak electrolyte ? Explain with an example.
Answer:
(A) Statement of Kohlrausch’s law : This states that at infinite dilution of the solution, each ion of an electrolyte migrates independently of its co-ions and contributes independently to the total molar conductivity of the electrolyte, irrespective of the nature of other ions present in the solution.

(B) Explanation : Both the ions, cation and anion of the electrolyte make a definite contribution to the molar conductivity of the electrolyte at infinite dilution or zero concentration (∧₀).
If \(\lambda_{+}^{0}\) and \(\lambda_{-}^{0}\) are the molar ionic conductivities of cation and anion respectively at infinite dilution, then
∧₀ = \(\lambda_{+}^{0}\) + \(\lambda_{-}^{0}\).
This is known as Kohlrausch’s law of independent migration of ions.
For an electrolyte, B_xA_y giving x number of cations and y number of anions,
∧₀ = x\(\lambda_{+}^{0}\) + y\(\lambda_{-}^{0}\).

(C) Applications of Kohlrausch’s law :
(1) With this law, the molar conductivity of a strong electrolyte at zero concentration can be determined. For example,
\(\wedge_{0(\mathrm{KCl})}=\lambda_{\mathrm{K}^{+}}^{0}-\lambda_{\mathrm{Cl}^{-}}^{0}\)
(2) ∧₀ values of weak electrolyte with those of strong electrolytes can be obtained. For example,

Molar conductivity of a weak electrolyte at infinite dilution or zero concentration cannot be measured experimentally.
Consider the molar conductivity (∧₀) of a weak acid, CH₃COOH at zero concentration. By Kohlrausch s law,

where λ⁰CH₃COO^– and λ⁰_H⁺ are the molar ionic conductivities of CH₃COO^– and H⁺ ions respectively.
If ∧_0CH3COONa, ∧_0HCl and ∧_0NaCl are molar conductivities of CH₃COONa, HCl and NaCl respectively at zero concentration, then by
Kohlrausch’s law,

Hence, from ∧₀ values of strong electrolytes, ∧₀ of a weak electrolyte CH₃COOH, at infinite dilution can be calculated.

Question ii.
Explain electrolysis of molten NaCl.
Answer:
(1) Construction of an electrolytic cell : It consists of a vessel containing molten (fused) NaCl. Two graphite (carbon) inert electrodes are dipped in it, and connected to an external source of direct electric current (battery). The electrode connected to a negative terminal of the battery is a cathode and that connected to a positive terminal is an anode.

(2) Working of the cell :
(A) In the external circuit, the electrons flow through the wires from anode to cathode of the cell.
(B) The fused NaCl dissociates to form cations (Na⁺) and anions (Cl^–).
\(\mathrm{NaCl}_{\text {(fused) }} \longrightarrow \mathrm{Na}_{(\mathrm{l})}^{+}+\mathrm{Cl}_{(\mathrm{l})}^{-}\)
Na⁺ migrate towards cathode and Cl^– migrate towards anode.

Fig. 5.7 : Electrolysis of fused sodium chloride

(C) Reactions in electrolytic cell :
(i) Reduction half reaction at cathode : The Na⁺ ions get reduced by accepting electrons from a cathode supplied by a battery and form metallic sodium.
\(\mathrm{Na}^{+}+\mathrm{e}^{-} \longrightarrow \mathrm{Na}_{(\mathrm{s})} \text { (reduction) }\)

(ii) Oxidation half reaction at anode : The Cl^– ions get oxidised by giving up electrons to the anode forming neutral Cl atoms in the primary process, and these Cl atoms combine forming Cl₂ gas in the secondary process.

The released electrons in the anodic oxidation half reaction return to battery through the metallic wires.

Net cell reaction : In order to maintain the electrical neutrality, the number of electrons gained at cathode must be equal to the number of electrons released at anode. Hence the reduction half reaction is multiplied by 2 and both reactions, oxidation half reaction and reduction half reaction are added to obtain a net cell reaction.

Results of electrolysis :

• A molten silvery white Na is formed at cathode which floats on the surface of molten NaCl.
• A pale green Cl₂ gas is liberated at anode.

Question iii.
What current strength in amperes will be required to produce 2.4g of Cu from CuSO₄ solution in 1 hour ? Molar mass of Cu = 63.5 g mol^-1.
Answer:
Given : W_Cu = 2.4 g; t = 1 hr = 1 × 60 × 60 s
M_Cu = 63.5 g mol^-1; I = ?

Ans. Current strength = I = 2.026 A

Question iv.
Equilibrium constant of the reaction,
2Cu⁺_(aq) → Cu²⁺_(aq) + Cu_(s)
is 1.2 × 10⁶. What is the standard potential of the cell in which the reaction takes place ?
Answer:
For the cell reaction, n = 1

Question v.
Calculate emf of the cell
Zn_(s)|Zn²⁺ (0.2M)||H⁺(1.6M)|H₂(g, 1.8 atm)|Pt at 25°C.
Answer:
Given : Zn_(s)|Zn²⁺(0.2M)||H⁺(1.6M)|H₂(g, 1.8 atm)|Pt


= 0.763 – 0.0296 × (- 0.8521)
= 0.763 + 0.02522
= 0.7882
Ans. \(E_{\text {cell }}^{0}\) = 0.7882 V

Question vi.
Calculate emf of the following cell at 25°C.
Zn_(s)| Zn²⁺(0.08M)||Cr³⁺(0.1M)|Cr
E⁰_Zn = – 0.76 V, E⁰_Cr = – 0.74 V
Answer:

Question vii.
What is a cell constant ? What are its units? How is it determined experimentally?
Answer:
(A) Cell constant of a conductivity cell is defined as the ratio of the distance between the electrodes divided by the area of cross section of the electrodes.

In SI units it is expected as m^-1.

The resistance of an electrolytic solution is measured by using a conductivity cell and Wheatstone

Fig. 5.6 : Measurement of conductance
The measurement of molar conductivity of a solution involves two steps as follows :
Step I : Determination of cell constant of the conductivity cell :
KCl solution (0.01 M) whose conductivity is accurately known (κ = 0.00141 Ω^-1 cm^-1) is taken in a beaker and the conductivity cell is dipped. The two electrodes of the cell are connected to one arm while the variable known resistance (R) is placed in another arm of Wheatstone bridge.

A current detector D’ which is a head phone or a magic eye is used. J is the sliding jockey (contact) that slides on the arm AB which is a wire of uniform cross section. A source of A.C. power (alternating power) is used to avoid electrolysis of the solution.

By sliding the jockey on wire AB, a balance point (null point) is obtained at C. Let AC and BC be the lengths of wire.

If R_solution is the resistance of KCl solution and R_x is the known resistance then by Wheatstone’s bridge principle,
\(\frac{R_{\text {solution }}}{\mathrm{BC}}=\frac{R_{x}}{\mathrm{AC}}\)
∴ \(R_{\text {solution }}=\mathrm{BC} \times \frac{R_{x}}{\mathrm{AC}}\)
Then the cell constant ‘ b ’ of the conductivity cell is obtained by, b = κ_Kcl × R_solution.

Step II : Determination of conductivity of the given solution :
KCl solution is replaced by the given electrolytic solution and its resistance (R_s) is measured by Wheatstone bridge method by similar manner by obtaining a null point at D.
The conductivity (κ) of the given solution is,
κ = \(\frac{\text { cell constant }}{R_{\mathrm{s}}}=\frac{b}{R_{\mathrm{s}}}\)

Step III: Calculation of molar conductivity :
The molar conductivity (∧_m) is given by,

Since the concentration of the solution is known, ∧_m can be calculated.

Question viii.
How will you calculate the moles of electrons passed and mass of the substance produced during electrolysis of a salt solution using reaction stoichiometry.
Answer:
Calculation of moles of electrons passed : The charge carried by one mole of electrons is referred to as one faraday (F). If total charge passed is Q C, then moles of electrons passed = \(\frac{Q(\mathrm{C})}{F\left(\mathrm{C} / \mathrm{mol} \mathrm{e}^{-}\right)}\)

Calculation of mass of product : Mass, W of product formed is given by,
W = moles of product × molar mass of product (M)
= \(\frac{Q}{96500}\) × mole ratio × M
= \(\frac{I \times t}{96500}\) × mole ratio × M 96500
When two electrolytic cells containing different electrolytes are connected in series so that same quantity of electricity is passed through them, then the masses W₁ and W₂ of products produced are given by,

Question ix.
Write the electrode reactions when lead storage cell generates electricity. What are the anode and cathode and the electrode reactions during its recharging?
Answer:
Recharging of the cell : When the discharged battery is connected to external electric source and a higher external potential is applied the cell reaction gets reversed generating H₂SO₄.
Reduction at the – ve electrode or cathode :
\(\mathrm{PbSO}_{4(\mathrm{~s})}+2 \mathrm{e}^{-} \rightarrow \mathrm{Pb}^{(s)}+\mathrm{SO}_{4(\mathrm{aq})}^{2-}\)
Oxidation at the + ve electrode or anode :

The emf of the accumulator depends only on the concentration of H₂SO₄.

Question x.
What are anode and cathode of H₂-O₂ fuel cell ? Name the electrolyte used in it. Write electrode reactions and net cell reaction taking place in the fuel cell.
Answer:
Construction :
(i) In fuel cell the anode and cathode are porous electrodes with suitable catalyst like finely divided platinum.

(iii) H₂ is continuously bubbled through anode while O, gas is bubbled through cathode.

Working (cell reactions) :
(i) Oxidation at anode : At anode, hydrogen gas is oxidised to H₂O.
2H_2(g) + 4OH^–_(aq) → 4H₂O_(l) + 4e^– (oxidation half reaction)
(ii) Reduction at cathode : The electrons released at anode travel to cathode through external circuit and reduce oxygen gas to OH^–.
O_2(g) + 2H₂O_(l) + 4e^– → 4OH^–_(aq) (reduction half reaction)

(iii) Net cell reaction: Addition of both the above reactions at anode and cathode gives a net cell reaction.
2H_2(g) + O_2(g) → 2H₂O_(l) (overall cell reaction)

Question xi.
What are anode and cathode for Leclanche’ dry cell ? Write electrode reactions and overall cell reaction when it generates electricity.
Answer:
A dry cell has zinc vessel as anode and graphite rod as cathode and moist paste of ZnCl₂, MnO₂, NH₄Cl as electrolytes.
At anode :
Zn_(s) → \(\mathrm{Zn}_{(\mathrm{aq})}^{2+}\) + 2e^– (Oxidation half reaction)
At graphite (c) cathode :
\(2 \mathrm{NH}_{4(\mathrm{e})}^{+}\) + 2e^– → 2NH_3(aq) + H_2(g) (Reduction half reaction)
2MnO_2(s) + H₂ → Mn₂O_3(s) + H₂O_(l)
There is a side reaction inside the cell, between Zn²⁺ ions and aqueous NH₃.
\(\mathrm{Zn}_{(\mathrm{aq})}^{2+}+4 \mathrm{NH}_{3(\mathrm{aq})} \longrightarrow\left[\mathrm{Zn}\left(\mathrm{NH}_{3}\right)_{4}\right]_{(\mathrm{aq})}^{2+}\)

Question xii.
Identify oxidising agents and arrange them in order of increasing strength under standard state conditions. The standard potentials are given in parenthesis.
Al(- 1.66 V), Cl₂ (1.36 V), Cd²⁺ (-0.4 V), Fe (-0.44 V), I₂ (0.54 V), Br^– (1.09 V).
Answer:
The oxidising agents are I₂, Br^– and Cl₂. The increasing strength is

(Note : Actually Br₂ acts as an oxidising agent but not Br^–.)

Question xiii.
Which of the following species are reducing agents? Arrange them in order of increasing strength under standard state conditions. The standard potentials are given in parenthesis.
K (-2.93V), Br₂(1.09V), Mg(-2.36V), Co³⁺(1.61V), Ti²⁺(-0.37V), Ag⁺(0.8V), Ni (-0.23V).
Answer:
Lower the standard reduction potential, higher is reducing power. The reducing agents are Ni, Mg and K. Their increasing strength is,

(Note : Cations don’t act as reducing agent since they are already in oxidised state.)

Question xiv.
Predict whether the following
reactions would occur spontaneously
under standard state conditions.
a. Ca_(s) + Cd²⁺_(aq) → Ca²⁺_(aq) + Cd_(s)
b. 2 Br-_(s) + Sn²⁺(aq) → Br_2(l) + Sn_(s)
c. 2Ag_(s) + Ni²⁺_(aq) → 2 Ag⁺_(aq) + Ni_(s)
(use information of Table 5.1)
Answer:

12th Chemistry Digest Chapter 5 Electrochemistry Intext Questions and Answers

Question 1.
How does electrical resistance depend on the dimensions of an electronic (metallic) conductor?
Answer:
The electrical resistance of an electronic conductor is linearly proportional to its length (l) and inversely proportional to its cross section area a.

Fig. 5.3 : Electronic conductor
Thus, R ∝ l; R ∝ \(\frac{1}{a}\)
∴ R ∝ \(\frac{l}{a}\) or R = ρ × \(\frac{l}{a}\)
where the proportionality constant p is called specific resistance. IUPAC recommends the term resistivity for specific resistance.

Question 2.
What are the units of resistivity ?
Answer:
For an electronic conductor of length l, and cross section area a, the resistance R is represented as
R = ρ × \(\frac{l}{a}\)
where ρ is the resistivity of the conductor.
∴ ρ = R × \(\frac{a}{l}\)
If l = 1 m, a = 1 m², ρ = R

Hence, resistivity is the resistance of a conductor of volume of 1 m³.
(In C.G.S. units, the units of ρ are ohm cm. Hence, ρ is the resistance of a conductor of unit volume or 1 cm³.)

Question 3.
Define resistivity. What are its units ?
Answer:
Resistivity (or specific resistance) : It is the resistance of a conductor that is 1 m in length and 1 m² in cross section area in SI units. (In C.G.S. units, it is the resistance of a conductor that is 1 cm in length and 1 cm² in cross section area.) Hence, the resistivity is the resistance of a conductor of unit volume. (In case of electrolytic solution, ρ is the resistivity i.e., resistance of a solution of unit volume.)
It has SI units, ohm m and C.G.S. units, ohm cm.

Question 4.
Why is alternating current used in the measurement of conductivity of the solution ?
Answer:
If direct current (D.C.) by battery is used, there will be electrolysis and the concentration of the solution is changed. Hence alternating current (A.C.) with high frequency is used.

Try this… (Textbook page No. 93)

Question 1.
What must be the concentration of a solution of silver nitrate to have the molar conductivity of 121.4 Ω^-1 cm² mol^-1 and the conductivity of 2.428 × 10^-3 Ω^-1 cm^-1 at 25 °C ?
Answer:

∴ Concentration of a Solution = 0.02 M

Try this… (Textbook page No. 96)

Question 1.
Obtain the expression for dissociation constant in terms of ∧_c and ∧₀ using Ostwald’s dilution law.
Answer:
Consider a solution of a weak electrolyte, BA having concentration C mol dm^-3. If α is the degree of dissociation, then by Ostwald’s theory of weak electrolytes,

If K is the dissociation constant of the weak electrolyte, then by Ostwald’s dilution law,
K = \(\frac{\alpha^{2} C}{(1-\alpha)}\)
If ∧_m is the molar conductivity of the electrolyte BA at the concentration C and ∧₀ is the molar conductivity at zero concentration or infinite dilution, then

Hence by measuring ∧_m at the concentration C and knowing ∧₀, the dissociation constant can be calculated.
If \(\lambda_{+}^{0}\) and \(\lambda_{-}^{0}\) are the ionic conductivities, then by Kohlrauseh’s law, ∧₀ = \(\lambda_{+}^{0}\) + \(\lambda_{-}^{0}\).

Learn this as well…

Question 1.
How is the cell constant of a conductivity cell determined?
Answer:
The cell constant of a given conductivity cell is obtained by measuring the resistance (R) (or the conductance) of a standard solution whose conductivity (f_c) is accurately known by using Wheatstone’s bridge (discussed in Q. 37). For this purpose, KCl solution of accurately known conductivity is used.
\(\kappa_{\mathrm{KCl}}=\frac{1}{R_{\mathrm{KCl}}} \times \frac{l}{a}\) where \(\frac{l}{a}\) is a cell constant, represented by b.
∴ \(\kappa_{\mathrm{KCl}}=\frac{b}{R_{\mathrm{KCl}}}\)
or b = κ_KCl × R_KCl
For example, the conductivity of 0.01 M KCl is 0.00141 Ω^-1 cm^-1 (S cm^-1). Hence by measuring R KCl the cell constant b can be obtained.

Try this… (Textbook page No. 95)

Question 1.
Calculate ∧₀ (CH₂ClCOOH) if ∧₀ values for HCl, KCl and CH₂ClCOOK are respectively, 4.261, 1.499 and 1.132 Ω^-1 m² mol^-1.
Solution :

Adding equations (i) and (ii) and subtracting equation (iii) we get equation (I).

Can you tell ? (Textbook page No. 103)

Question 1.
You have learnt Daniel cell in XIth standard. Write notations for anode and cathode. Write the cell formula.
Answer:
Daniel cell is represented as,

Try this… (Textbook page No. 104)

Question 1.
Write electrode reactions and overall cell reaction for Daniel cell you learnt in standard XI.
Answer:
Reactions for Daniell cell:

Question 1.
Describe different types of reversible electrodes with examples. (1 mark for each type)
Answer:
A reversible electrochemical cell or a galvanic cell consists of two reversible half cells or electrodes. There are four types of reversible electrodes according to their compositions.
(1) Metal-metal ion electrode : This electrode is set up by dipping a metal in a solution containing its own ions, e.g. Zn rod dipped into ZnSO₄ solution containing Zn⁺⁺ ions of concentration C.
It is represented as,
\(\mathrm{Zn}^{2+}{ }_{(\mathrm{aq})} \mid \mathrm{Zn}_{(\mathrm{s})}\)
The reduction reaction at the electrode is,
Zn⁺⁺_(aq) + 2e^– → Zn_(s)

(2) Metal-sparingly soluble salt electrode : This electrode consists of a metal coated with one of its sparingly soluble salts and immersed in a solution containing an electrolyte having a common anion as that of the salt. For example, silver electrode coated with sparingly soluble AgCl dipped in KCl solution with common anion Cl^–. This electrode is represented as,
Cl^–_(aq) | AgCl_(s) | Ag_(s)
The reduction reaction is,
AgCl_(s) + e → Ag_(s) + Cl^–_(aq)

(3) Gas electrode : This is developed by bubbling pure and dry gas around a platinised platinum foil dipped in the solution containing ions (of the gas) reversible with respect to the gas bubbled.
The gas is adsorbed on the surface of platinum foil and establishes an equilibrium with its ions in the solution. Pt electrode provides electrical contact and also acts as a catalyst.
Some of the gas electrodes are represented as follows :
(i) Hydrogen gas electrode :
H⁺_(aq) | H₂(g, P_H2) | Pt
Reduction reaction : H⁺_(aq) + e^– → \(\frac {1}{2}\)H_2(g)
(ii) Chlorine gas electrode :
Cl^–_(aq) | Cl₂(g, PCl₂) | Pt
Reduction reaction : \(\frac {1}{2}\)Cl_2(g) + e- → Cl^–_(aq)

(4) Redox electrode (Oxidation reduction electrode) : This electrode consists of a platinum wire dipped in a solution containing the ions of the same metal (or a substance) in two different oxidation states, like Fe²⁺ – Fe³⁺, Sn²⁺ – Sn⁴⁺, Mn⁺⁺ – MnO^–₄, etc.
A platinum electrode which provides an electrical contact and acts as catalyst aquires an equilibrium between two ions in the solution, due to their tendency to undergo a change from one oxidation state to another. The electrodes are represented as,
Fe²⁺_(aq), Fe³⁺_(aq) | Pt
Reduction reaction : Fe³⁺_(aq) + e^– → Fe²⁺_(aq)
SnCl_2(aq), SnCl_4(aq) | Pt
Reduction reaction : Sn⁴⁺_(aq) + 2e^– →Sn²⁺_(aq)

Use your brain power! (Textbook page No. 98)

Question 1.
Distinguish between electrolytic and galvanic cells.
Answer:
Electrolytic cell:

1. This device is used to bring about a non-spontaneous chemical reaction by passing an electric current.
2. It is used to bring about a chemical reaction generally for the dissociation (electrolysis) of compounds.
3. In this cell, electrical energy is converted into chemical energy.
4. In this cell, the cathode is negative and the anode is positive.
5. Electrolytic cells are irreversible.
6. Oxidation takes place at the positive electrode and reduction at the negative electrode.
7. The electrons are supplied by the external source and enter through cathode and come out through anode.
8. It is used for electroplating, electrorefining, etc.

Electrochemical cell (Galvanic cell or Voltaic cell):

1. This device is used to produce electrical energy by a spontaneous chemical reaction.
2. It is used to generate electricity.
3. In this cell, chemical energy is converted into electrical energy.
4. In this cell, the cathode is positive and the anode is negative.
5. Electrochernical cells are reversible.
6. Oxidation takes place at the negative electrode and reduction at the positive electrode.
7. The electrons move from anode to cathode in the external circuit.
8. It is used as a source of electric current.

Try this… (Textbook page No. 107)

Question 1.
Write expressions to calculate equilibrium constant from
i. Concentration data
ii. Thermochemical data
iii. Electrochemical data
Answer:
(i) Consider following a reversible cell reaction.
aA + bB ⇌ cC + dD
If [A], [B], [C] and [D] represent concentrations of reactants and products then the equilibrium constant K is,
K = \(\frac{[\mathrm{C}]^{c} \times[\mathrm{D}]^{d}}{[\mathrm{~A}]^{a} \times[\mathrm{B}]^{b}}\)
(ii) If ΔG⁰ is the standard Gibbs free energy change at temperature T then,
ΔG⁰ = – RTlnK = – 2.303 RTlog₁₀K
(iii) From electrochemical data,
if \(E_{\text {cell }}^{0}\) is the standard cell potential and K is the equilibrium constant for the cell reaction at a temperature T, then,
\(E_{\text {cell }}^{0}=\frac{0.0592}{n} \log _{10} K\)

Learn this as well…

Question 1.
The construction and working of the calomel electrode.
Answer:
(1) Since standard hydrogen electrode (SHE) is not convenient for experimental use, a secondary reference electrode like calomel electrode is used.
(2) Construction : It consists of a glass vessel with side arm B for dipping in a desired solution of another electrode like, ZnSO_4(aq) for an electric contact. The vessel is filled with mercury, a paste of Hg and Hg₂Cl₂ (calomel) and saturated KCl solution.

Fig. 5.15 : Determination of standard electrode potential using calomel electrode
(3) The potential developed depends upon the concentration of Cl^– or KCl solution. When saturated KCl solution is used, its reduction potential is 0.242 V.
(4) Consider following cell :
Zn_(s) | ZnSO_4(aq) || KCl_(aq) | Hg₂Cl_2(s) | Hg
OR Zn_(s) | ZnSO_4(aq) || Calomel electrode
Reduction reaction for calomel electrode :
Hg₂Cl_2(s) + 2e^– → 2Hg_(l) + 2Cl^–_(aq)
Hence potential of calomel electrode depends on the concentration of Cl^– or KCl solution.

Can you tell ? (Textbook page No. 114)

Question 1.
In what ways are fuel cells and galvanic cells similar and in what ways are they different ?
Answer:
Similarity between fuel cells and galvanic cells :

• In both the cells, there is oxidation at anode and j reduction at cathode.
• The cell potential is developed due to net redox reactions.
• Both are galvanic cells.

Difference in fuel cells and galvanic cells :

• Fuel cells involve electrodes with large surface area while galvanic cells involve electrodes with j compact surface area.
• Fuel cells involve gaseous materials on a large scale while galvanic cells involve gaseous materials at a definite pressures along with electrolytes or there may not be gases.
• In fuel cells, the cell potential is developed due to exothermic combustion reactions while in galvanic cell, cell potential is developed due to normal redox reactions.
• In fuel cells gaseous electrode materials are continuously supplied from outside while in galvanic cells electrode materials have constant concentration or may change due to reactions.

Use your brain power (Textbook page No. 114)

Question 1.
Indentify the strongest and the weakest oxidizing agents from the electrochemical series.
Answer:
From the electrochemical series,
(a) The strongest oxidising agent is fluorine since it has the highest standard reduction potential (\(E_{\mathrm{F}_{2} / \mathrm{F}^{-}}^{0}\) = + 2.87 V).
(b) The weakest oxidising agent (or the strongest reducing agent) is lithium since it has the lowest standard reduction potential, (\(E_{\mathrm{Li}^{+} / \mathrm{Li}}^{0}\) = -3.045 V).

Use your brainpower (Textbook page No. 115)

Question 1.
Identify the strongest and the weakest reducing agents from the electrochemical series.
Answer:
(a) From the electrochemical series, the strongest reducing agent is lithium since it has the lowest standard reduction potential (\(E_{\mathrm{Li}^{+} / \mathrm{Li}}^{0}\) = -3.045 V).
(b) The weakest reducing agent is fluorine since it has the highest standard reduction potential,
(\(E_{\mathrm{F}_{2} / \mathrm{F}^{-}}^{0}\) = +2.87 V).

Question 2.
From E° values given in Table 5.1, predict whether Sn can reduce I₂ or Ni²⁺.
Answer:
From the electrochemical series,

Maharashtra State Board 12th Std Chemistry Textbook Solutions

• Solid State Class 12 Chemistry Textbook Solutions
• Solutions Class 12 Chemistry Textbook Solutions
• Ionic Equilibria Class 12 Chemistry Textbook Solutions
• Chemical Thermodynamics Class 12 Chemistry Textbook Solutions
• Electrochemistry Class 12 Chemistry Textbook Solutions
• Chemical Kinetics Class 12 Chemistry Textbook Solutions
• Elements of Groups 16, 17 and 18 Class 12 Chemistry Textbook Solutions
• Transition and Inner Transition Elements Class 12 Chemistry Textbook Solutions

Chemical Thermodynamics Class 12 Exercise Question Answers Solutions Maharashtra Board

Balbharti Maharashtra State Board 12th Chemistry Textbook Solutions Chapter 4 Chemical Thermodynamics Textbook Exercise Questions and Answers.

Class 12 Chemistry Chapter 4 Exercise Solutions Maharashtra Board

Chemistry Class 12 Chapter 4 Exercise Solutions

1. Select the most appropriate option.

Question 1.
The correct thermodynamic conditions for the spontaneous reaction at all temperatures are
(a) ΔH < 0 and ΔS > 0
(b) ΔH > 0 and ΔS < 0
(c) ΔH < 0 and ΔS < 0
(d) ΔH < 0 and ΔS = 0
Answer:
(a) ΔH < 0 and ΔS > 0

Question ii.
A gas is allowed to expand in a well-insulated container against a constant external pressure of 2.5 bar from an initial volume of 2.5 L to a final volume of 4.5 L. The change in internal energy, ΔU of the gas will be
(a) -500 J
(b) +500J
(c) -1013 J
(d) +1013 J
Answer:
(a) -500 J

Question iii.
In which of the following, entropy of the system decreases ?
(a) Crystallisation of liquid into solid
(b) Temperature of crystalline solid is increased from 0 K to 115 K
(c) H_2(g) → 2H_(g)
(d) 2NaHCO_3(s) → Na₂CO_3(s) + CO_2(g) + H₂O_(g)
Answer:
(a) Crystallisation of liquid into solid

Question iv.
The enthalpy of formation for all elements in their standard states is
(a) unity
(b) zero
(c) less than zero
(d) different elements
Answer:
(b) zero

Question v.
Which of the following reactions is exothermic ?
(a) H_2(g) → 2H_(g)
(b) C(s) → C_(g)
(c) 2Cl_(g) → Cl_2(g)
(d) H₂O_(s) → H₂O_(l)
Answer:
(c) 2Cl_(g) → Cl_2(g)

Question vi.
6.24 g of ethanol are vaporized by supplying 5.89 kJ of heat. Enthalpy of vaporization of ethanol will be
(a) 43.4 kJ mol^-1
(b) 60.2 kJ mol^-1
(c) 38.9 kJ mol^-1
(d) 20.4 kJ mol^-1
Answer:
(a) 43.4 kJ mol^-1

Question vii.
If the standard enthalpy of formation of methanol is -238.9 kJ mol^-1 then entropy change of the surroundings will be
(a) -801.7 JK^-1
(b) 801.7 JK^-1
(c) 0.8017 JK^-1
(d) -0.8017 JK^-1
Answer:
(b) 801.7 JK^-1

Question viii.
Which of the following are not state functions ?
1. Q + W 2. Q 3. W 4. H-TS
(a) 1, 2 and 3
(b) 2 and 3
(c) 1 and 4
(d) 2, 3 and 4
Answer:
(b) 2 and 3

Question ix.
For vaporization of water at 1 bar, ΔH = 40.63 kJ mol^-1 and ΔS =108.8 JK^-1 mol^-1. At what temperature, ΔG = 0?
(a) 273.4 K
(b) 393.4 K
(c) 373.4 K
(d) 293.4 K
Answer:
(c) 373.4 K

Question x.
Bond enthalpies of H – H, Cl – Cl and H – Cl bonds are 434 kJ mol^-1, 242 kJ mol^-2 and 431 kJ mol^-1, respectively. Enthalpy of formation of HCl is
(a) 245 kJ mol^-1
(b) -93 kJ mol^-1
(c) -245 kJ mol^-1
(d) 93 kJ mol^-1
Answer:
(b) -93 kJ mol^-1

2. Answer the following in one or two sentences.

Question i.
Comment on the statement: No work is involved in an expansion of a gas in vacuum.
Answer:
(1) When a gas expands against an external pressure Pex, changing the volume from V₁ to V₂, the work obtained is given by
W = -P_ex (V₂ – V₁).
(2) Hence the work is performed by the system when it experiences the opposing force or pressure.
(3) Greater the opposing force, more is the work.
(4) In free expansion, the gas expands in vaccum where it does not experience opposing force, (P = 0). Since external pressure is zero, no work is obtained.
∴ W = -P_ex (V₂ – V₁)
= -0 × (V₂ – V₁)
= 0
(5) Since during expansion in vacuum no energy is expended, it is called free expansion.

Question ii.
State the first law of thermodynamics.
Answer:
The first law of thermodynamics is based on the principle of conservation of energy and can be stated in different ways as follows :

1. Energy can neither be created nor destroyed, however, it may be converted from one form into another.
2. Whenever, a quantity of one kind of energy is consumed or disappears, an equivalent amount of another kind of energy appears.
3. The total mass and energy of an isolated system remain constant, although there may be interconservation of energy from one form to another.
4. The total energy of the universe remains constant.

Question iii.
What is enthalpy of fusion?
Answer:
Enthalpy of fusion (Δ_fusH) : The enthalpy change that accompanies the fusion of one mole of a solid into a liquid at constant temperature and pressure is called enthalpy of fusion.
For example,

This equation describes that when one mole of ice melts (fuses) at 0 °C (273 K) and 1 atmosphere, 6.1 kJ of heat will be absorbed.

Question iv.
What is standard state of a substance?
Answer:
The thermodynamic standard state of a substance (compound) is the most stable physical state of it at 298 K and 1 atmosphere (or 1 bar). The enthalpy of the substance in the standard state is represented as Δ_fH⁰.

Question v.
State whether ∆S is positive, negative or zero for the reaction 2H_(g) → H_2(g). Explain.
Answer:
(i) The given reaction, 2H_(g) → H_2(g) is the formation of H_2(g) from free atoms.
(ii) Since two H atoms form one H₂ molecule, ∆n = 1 – 2= -1 and disorder is decreased. Hence entropy change ∆S < 0 (or negative).

Question vi.
State second law of thermodynamics in terms of entropy.
Answer:
The second law of thermodynamics states that the total entropy of the system and its surroundings (universe) increases in a spontaneous process.
OR
Since all the natural processes are spontaneous, the entropy of the universe increases.
It is expressed mathematically as
∆ S_Total = ∆ S_system + ∆S_surr > 0
∆ S_Universe = ∆ S_system + ∆ S_surr > 0

Question vii.
If the enthalpy change of a reaction is ∆H how will you calculate entropy of surroundings?
Answer:
(i) For endothermic reaction, ∆H > 0. This shows the system absorbs heat from surroundings.
∴ ∆_surr H < 0.
∵ Entropy change = ∆_surr S = \(\frac{-\Delta_{\text {surr }} H}{T}\)
There is decrease in entropy of surroundings.
(ii) For exothermic reaction, ∆H < 0, hence for surroundings, ∆_surr H > 0

∴ ∆_surr > 0.

Question viii.
Comment on spontaneity of reactions for which ∆H is positive and ∆S is negative.
Answer:
Since ∆H is +ve and ∆S is -ve, ∆G will be +ve at all temperatures. Hence reactions will be non-spontaneous at all temperatures.

3. Answer in brief.

Question i.
Obtain the relationship between ∆G° of a reaction and the equilibrium constant.
Answer:
Consider following reversible reaction, aA + bB ⇌ cC + dD
The reaction quotient Q is,
Q = \(\frac{[\mathrm{C}]^{c} \times[\mathrm{D}]^{d}}{[\mathrm{~A}]^{a} \times[\mathrm{B}]^{b}}\)
The free energy change ∆G for the reaction is ∆G = ∆G° + RT in Q
Where ∆G° is the standard free energy change.
At equilibrium
Q = \(\frac{[\mathrm{C}]_{e}^{c} \times[\mathrm{D}]_{e}^{d}}{[\mathrm{~A}]_{e}^{a} \times[\mathrm{B}]_{e}^{b}}=\mathrm{K}\)
∴ ∆G = ∆G° + RT In K
∵ at equilibrium ∆G = 0
∴ 0 = AG° + RT In K
∴ ∆G° = -RT In K
∴ ∆G°= -2.303 RT log₁₀K.

Question ii.
What is entropy? Give its units.
Answer:
(i) Entropy : Being a state function and thermodynamic function it is defined as entropy change (∆S) of a system in a process which is equal to the amount of heat transferred in a reversible manner (Q_rev) divided by the absolute temperature (T), at which the heat is absorbed. Thus,

(ii) Units of entropy are JK^-1 in SI unit and cal K^-1 in c.g.s. units. It is also expressed in terms of entropy unit (e.u.). Hence 1 e.u. = 1 JK^-1.
(iii) Entropy is a measure of disorder in the system. Higher the disorder, more is entropy of the system.

Question iii.
How will you calculate reaction enthalpy from data on bond enthalpies?
Answer:
(i) In chemical reactions, bonds are broken in the reactant molecules and bonds are formed in the product molecules.
(ii) Energy is always required to break a chemical bond while energy is always released in the formation of the bond.
(iii) The enthalpy change of a gaseous reactions (Δ_fH⁰) involving substances with covalent bonds can be calculated with the help of bond enthalpies of reactants and products. (In case of solids we need lattice energy or heat of sublimation while in case of liquids we need heat of evaporation.)

If the energy required to break the bonds of reacting molecules is more than the energy released in the bond formation of the products, then the reaction will be endothermic and ∆H⁰ reaction will be positive. On the other hand if the energy released in the bond formation of the products is more than the energy required to break the bonds of reacting molecules then the reaction will be exothermic and ∆H⁰ reaction will be negative.

Question iv.
What is the standard enthalpy of combustion ? Give an example.
Answer:
Standard enthalpy of combustion or standard heat of combustion : it is defined as the enthalpy change when one mole of a substance in the standard state undergoes complete combustion in a sufficient amount of oxygen at constant temperature (298 K) and pressure (1 atmosphere or 1 bar). It is denoted by ∆_cH⁰.
E.g. CH₃OH_(l) + \(\frac {3}{2}\) O_2(g) = CO_2(g) + 2H₂O
∆_cH⁰= -726 kJ mol^-1
(∆_cH⁰ is always negative.)
[Note : Calorific value : It is the enthalpy change or amount of heat liberated when one gram of a substance undergoes combustion.

Question v.
What is the enthalpy of atomization? Give an example.
Answer:
Enthalpy of atomisation (∆_atomH) : it is the enthalpy change accompanying the dissociation of one mole of gaseous substance into its atoms at constant temperature and pressure.
For example : CH_4(g) → C_(g) + 4H_(g) ∆_atomH = 1660 kJ mol^-1

Question vi.
Obtain the expression for work done in chemical reaction.
Answer:
Consider n₁ moles of gaseous reactants A of volume V₁ change to n₂ moles of gaseous products B of volume V₂ at temperature T and pressure P.

In the initial state, PV₁ = n₁RT
In the final state, PV₂ = n₂RT
PV₂ – PV₁ = n₂RT – n₁RT = (n₂ – n₁)RT = ∆nRT
where ∆n is the change in number of moles of gaseous products and gaseous reactants.
Due to net changes in gaseous moles, there arises change in volume against constant pressure resulting in mechanical work, -P∆V.
∴ W = -P∆V = -P(V₂ – V₁) = – ∆nRT
(i) If n₁ – n₂, ∆n = 0, W = 0. No work is performed.
(ii) If n₂ > n₁, ∆n > 0, there is a work of expansion by the system and W is negative.
(iii) If n₂ < n₁, ∆n < 0, there is a work of compression, hence work is done on the system and W is positive.

Question vii.
Derive the expression for PV work.
Answer:
Consider a certain amount of an ideal gas enclosed in an ideal cylinder fitted with massless, frictionless rigid movable piston at pressure P, occupying volume V₁ at temperature T.

Fig. 4.8 : Work of expansion
As the gas expands, it pushes the piston upward through a distance d against external force F, pushing the surroundings.
The work done by the gas is,
W = opposing force × distance = -F × d
-ve sign indicates the lowering of energy of the system during expansion.
If a is the cross section area of the cylinder or piston, then,
W = \(-\frac{F}{a}\) × d × a
Now the pressure is P_ex = \(\frac{F}{a}\)
while volume change is, ΔV = d × a
∴ W = -P_ex × ΔV
If during the expansion, the volume changes from V₁ and V₂ then, ΔV = V₂ – V₁
∴ W= -P_ex(V₂ – V₁)
During compression, the work W is +ve, since the energy of the system is increased,
W = +P_ex(V₂ – V₁)

Question viii.
What are intensive properties? Explain why density is intensive property.
Answer:
(A) Intensive property : It is defined as a property of a system whose magnitude is independent of the amount of matter present in the system.
Explanation :

1. Intensive property is characteristic of the system, e.g., refractive index, density, viscosity, temperature, pressure, boiling point, melting point, freezing point of a pure liquid, surface tension, etc.
2. The intensive properties are not additive.

(B) Density is a ratio of two extensive properties namely, mass and volume. Since the ratio of two extensive properties represents an intensive property, density is an intensive property. It does not depend on the amount of a substance.

Question ix.
How much heat is evolved when 12 g of CO reacts with NO₂ ? The reaction is :
4 CO_(g) + 2 NO_2(g) → 4CO_2(g) + N_2(g), ∆H⁰ = -1200 kJ

4. Answer the following questions.

Question i.
Derive the expression for the maximum work.
Answer:

Consider n moles of an ideal gas enclosed in an ideal cylinder fitted with a massless and frictionless movable rigid piston. Let V be the volume of the gas at a pressure P and a temperature T.
If in an infinitesimal change pressure changes from P to P – dP and volume increases from V to V + dV. Then the work obtained is, dW = -(P-dP) dV
= -PdV + dPdV
Since dP.dV is negligibly small relative to PdV
dW= -PdV
Let the state of the system change from A(P₁, L₁) to B (P₂, V₂) isothermally and reversibly, at temperature T involving number of infinitesimal steps.

Then the total work or maximum work in the process is obtained by integrating above equation.

At constant temperature,

where n, P, V and T represent number of moles, pressure, volume and temperature respectively. For the process,
ΔU = 0, ΔH = 0.
The heat absorbed in reversible manner
Q_rev, is completely converted into work.
Q_rev = -W_max.
Hence work obtained is maximum.

Question ii.
Obtain the relatioship between ∆H and ∆U for gas phase reactions.
Answer:
Consider a reaction in which n₁ moles of gaseous reactant in initial state change to n₂ moles of gaseous product in the final state.
Let H₁, U₁, P₁, V₁ and H₂, U₂, P₂, V₂ represent enthalpies, internal energies, pressures and volumes in the initial and final states respectively then,

The heat of reaction is given by enthalpy change ΔH as,
ΔH = H₂ – H₁
By definition, H = U + PV
∴ H₁ = U₁ + P₁V₁ and H₂ = U₂+ P₂V₂
∴ ΔH = (U2 + P₂V₂) – (U₁ + P₁V₁)
= (U2 – U₁) + (P₂V₂ – P₁V₁)
Now, ΔU = U₂ – U₁
Since PV = nRT,
For initial state, P₁V₁= n₁RT
For final state, P₂V₂ = n₂RT
∴ P₂V₂ – P₁V₁ = n₂RT – n₁RT
= (n₂ – n₁) RT
= ΔnRT
where Δn

∴ ΔH = ΔU + ΔnRT
If Q_P and Q_V are the heats involved in the reaction at constant pressure and constant volume respectively, then since Q_P = ΔH and Q_V = ΔU.
∴ Q_P = Q_V = ΔnRT

Question iii.
State Hess’s law of constant heat summation. Illustrate with an example. State its applications.
Answer:
Statement of law of constant heat summation : It states that, the heat of a reaction or the enthalpy change in a chemical reaction depends upon initial state of reactants and final state of products and independent of the path by which the reaction is brought about (i.e. in single step or in series of steps).
OR
Heat of reaction is same whether it is carried out in one step or in several steps.
Explanation :
Consider the formation of CO_2(g).

Hess’s law treats thermochemical equations mathematically i.e., they can be added, subtracted or multiplied by numerical factors like algebraic equations.

Applications : Hess’s law is used for :

1. To calculate heat of formation, combustion, neutralisation, ionization, etc.
2. To calculate the heat of reactions which may not take place normally or directly.
3. To calculate heats of extremely slow or fast reactions.
4. To calculate enthalpies of reactants and products.

Question iv.
Although ∆S for the formation of two moles of water from H₂ and O₂ is -327 JK^-1, it is spontaneous. Explain. (Given ∆H for the reaction is -572 kJ).
Answer:
Given : ΔS= -327 JK^-1; ΔH = -572 kJ
ΔG = ΔH – TΔS, and ΔH << ΔS
∴ ΔG < 0, and hence the formation of H₂O_(l) is spontaneous.

Question v.
Obtain the relation between ∆G and ∆S_Total. Comment on spontaneity of the reaction.
Answer:
(i) Gibbs free energy, G is defined as,
G = H – TS
where H is the enthalpy, S is the entropy of the system at absolute temperature T.
Since H, T and S are state functions, G is a state function and a thermodynamic function.

(ii) At constant temperature and pressure, change in free energy ΔG for the system is represented as, ∆G = ∆H – T∆S

This is called Gibbs free energy equation for ∆G. In this ∆S is total entropy change, i.e., ∆S_Total.

(iii) The SI units of ∆G are J or kJ (or Jmol^-1 or kJmol^-1).
The c.g.s. units of ∆G are cal or kcal (or cal mol^-1 or kcal mol^-1.)

The second law explains the conditions of spontaneity as below :
(i) ∆S_total > 0 and ∆G < 0, the process is spontaneous.
(ii) ∆S_total < 0 and ∆G > 0, the process is nonspontaneous.
(iii) ∆S_total = 0 and ∆G = 0, the process is at equilibrium.

Question vi.
One mole of an ideal gas is compressed from 500 cm³ against a constant external pressure of 1.2 × 10⁵ Pa. The work involved in the process is 36.0 J. Calculate the final volume.
Answer:
Given : V₁ = 500 cm³ = 0.5 dm³;
P_ex = 1.2 × 10⁵ Pa = 1.2 bar; W= 36 J;
1 dm³ bar = 100 J; V₂ = ?
W = -P_ex (V₂ – V₁)
36 J = – 1.2 (V₂ – 0.5) dm³ bar
= -1.2 × 100 (V₂ – 0.5) J
∴ V₂ – 0.5 = \(\frac{-36}{1.2 \times 100}=-0.3\)
∴ V₂ = 0.5 -0.3 = 0.2 dm³ = 200 cm³
Ans. Final volume = 200 cm³.

Question vii.
Calculate the maximum work when 24g of O₂ are expanded isothermally and reversibly from the pressure of 1.6 bar to 1 bar at 298 K.
Answer:
Given : W₀₂ = 24 g, P₁ = 1.6 bar, P₂ = 1 bar
T = 298 K, W_max = ?

Question viii.
Calculate the work done in the decomposition of 132 g of NH₄NO₃ at 100 °C.
NH₄NO_3(s) → N₂O_(g) + 2 H₂O_(g)
State whether work is done on the system or by the system.
Answer:
NH4₄NO_3(s) → N₂O_(g) + 2 H₂O_(g)
m_NH4NO3 = 132 g; M_NH4NO3 = 80 g mol^-1
T = 273 + 100 = 373 K; Δn = ?
For the reaction,
Δn = Σn_{2 gaseous products} – Σn_{1 gaseous reactants}
= 3 – 0 = 3 mol
Since there is an increase in number of gaseous moles, the work is done by the system.
n_NH4NO3 = \(\frac{m_{\mathrm{NH}_{4} \mathrm{NO}_{3}}}{M_{\mathrm{NH}_{4} \mathrm{NO}_{3}}}\)
= \(\frac{132}{80}\)
= 1.65 mol
For 1 mol NH₄NO_3(s) Δn = 3 mol
∴ For 1.65 mol NH₄NO_3(s) Δn = 3 × 1.65 = 4.95 mol
W = -ΔnRT = -4.95 × 8.314 × 373
= – 15350 J
= – 15.35 kJ
Ans. Work is done by the system.
Work done = – 15.35 kJ

Question ix.
Calculate standard enthalpy of reaction,
Fe₂O_3(s) + 3CO_(g) → 2 Fe_(s) + 3CO_2(g),
from the following data.
∆_fH⁰(Fe₂O₃) = -824 kJ/mol,
∆_fH⁰(CO) = -110 kJ/mol,
∆_fH⁰(CO₂) = -393 kJ/mol
Answer:
Given : ∆_fH⁰Fe₂O₃ = -824 kJ/mol^-1;
∆_fH⁰(CO) = – 110 kJ mol^-1
∆_fH⁰(CO₂) = – 393 kJ/mol^-1; ∆_fH⁰ = ?
Required equation,
Fe₂O_3(s) + 3CO_(g) → 2Fe_(s) + 3CO_2(g)
∆H₁ = ? – (I)
Given equations :

= -(-824) -3 (-110) + 3(-393)
= 824 + 330 – 1179
∆_fH⁰ = -25 kJ
Ans. ∆_fH⁰ = -25 kJ

Question x.
For a certain reaction ∆H⁰ =219 kJ and ∆S⁰ = -21 J/K. Determine whether the reaction is spontaneous or nonspontaneous.
Answer:
Given : ∆H⁰ = 219 kJ; ∆S⁰ = -21 J/K, ∆G⁰ = ?
For standard state, T = 298 K
∆G⁰ = ∆H⁰ – T∆S⁰
= 219 – 298 × (-21) × 10^-3
= 219 + 6.258
= 225.3 kJ
Since ∆S < 0 and ∆G⁰ > 0, the reaction is non-spontaneous.

Question xi.
Determine whether the following reaction is spontaneous under standard state conditions.
2 H₂O_(l) + O_2(g) → 2H₂O_2(l)
if ∆H⁰ = 196 kJ, ∆S⁰ = -126 J/K
Does it have a cross-over temperature?
Answer:
Given : 2H₂O_(l) + O_2(g) → 2H₂O_2(l)
∆H⁰ = +196 kJ
∆S⁰ = -126 JK-1 =0.126 kj K-1
T= 298 K
∆G⁰ = ?
Cross over temperature = T = ?
∆G⁰ = ∆H⁰ – T∆S⁰
= 196 – 298 (-0.126)
= 196 + 37.55
= + 233.55 kJ
∵ ∆G⁰ > 0, the reaction is non-spontaneous.
∆H⁰ > 0, ∆S⁰ < 0,
Since at all temperatures, ∆G⁰ > 0, there is no cross over temperature.
Ans. The reaction is non-spontaneous.
There is no cross-over temperature for the reaction.

Question xii.
Calculate ∆U at 298 K for the reaction,
C₂H_4(g) + HCl_(g) → C₂H₅Cl_(g), ∆H = -72.3 kJ
How much PV work is done?
Answer:
Given : C₂H_4(g) + HCl_(g) → C₂H₅Cl_(g)
T = 298 K; ∆H = -72.3 kJ; PV = ?;
∆U = ?
∆n = Σn_{2gaseous products} – Σn_{1gaseous reactants}
= 1 – (1 + 1)= -1 mol
For PV work :
W = -∆nRT
= – (- 1) × 8.314 × 298
= 2478 J = 2.478 kJ
∆H = ∆U + ∆nRT
∴ ∆U = ∆H – ∆nRT
= – 72.3 – (-2.478)
= – 69.82 kJ
Ans. PV work = 2.478 kJ
∆U = -69.82 kJ

Question xiii.
Calculate the work done during synthesis of NH₃ in which volume changes from 8.0 dm3 to 4.0 dm³ at a constant external pressure of 43 bar. In what direction the work energy flows?
Answer:
Given : V₁ = 8.0 dm³; V₂ = 4.0 dm³; P_ex = 43 bar
W = ? What direction work energy flows ?
W = -P_ex(V₂ – V₁)
= -43 (4 – 8)
= 172 dm³ bar
= 172 × 100 J
= 17200 J
= 17.2 kJ
In this compression process, the work is done on the system and work energy flows into the system.

Question xiv.
Calculate the amount of work done in the
(a) oxidation of 1 mole HCl_(g) at 200 °C according to reaction.
4HCl_(g) + O_2(g) → 2 Cl_2(g) + 2 H₂O_(g)
(b) decomposition of one mole of NO at 300 °C for the reaction
2 NO_(g) → N_2(g) + O₂
Answer:
Given :
(a) 4HCl_(g) + O_2(g) → 2Cl_2(g) + 2H₂O_(g)
n_HCl = 1 mol; T = 273 + 200 = 473 K, W = ?
For 4 mol HCl ∆n = (2 + 2) – (4 + 1) = – 1 mol
∴ For 1 mol HCl ∆n = –\(\frac {1}{4}\) = -0.25 mol
W = -∆nRT = – (-0.25) × 8.314 × 473 = 983.11
(b) ∆n = (1 + 1) – 2 = 0 mol
W = -∆nRT = -(0) × 8.314 × 473 = 0
Ans. (a) W = 983.1 J
(b) W = 0.0 J

Question xv.
When 6.0 g of O₂ reacts with CIF as per
2CIF_(g) + O_2(g) → Cl₂O_(g) + OF_2(g)
The enthalpy change is 38.55 kJ. What is standard enthalpy of the reaction ?
Answer:
Given : The given reaction is for 1 mol O₂ or 32 g O₂.
∵ For 6.0 g O₂
∆ H⁰ = 38.55 kJ
∴ For 32 g O₂
∆ H⁰ = \(\frac{32 \times 38.55}{6}\)
= 205.6 kJ
Ans. ∆H⁰ = 205.6 kJ

Question xvi.
Calculate the standard enthalpy of formation of CH₃OH_(l) from the following data:
i. CH₃OH_(l) + \(\frac {3}{2}\) O_2(g) → CO_2(g) + 2H₂O_(l), ∆H⁰ = -726 kJ mol^-1
ii. C (Graphite) + O_2(g) → CO_2(g), ∆_cH⁰ = -393 kJ mol^-1
iii. H_2(g) + \(\frac {1}{2}\) O_2(g) → H₂O_(l), ∆_fH⁰ = -286 kJ mol^-1
Answer:


∴ ∆H⁰
= –\(\Delta H_{2}^{0}\) + \(\Delta H_{3}^{0}\) + 2∆\(\Delta H_{4}^{0}\)
= – (- 726) + (- 393) + 2(- 286)
= 726 – 393 – 572
= – 239 kJ mol^-1
Ans. Standard enthalpy of formation = ∆_fH⁰= -239 kJ mol^-1

Question xvii.
Calculate ∆H0 for the following reaction at 298 K
H₂B₄O_7(s) + H₂O_(l) → 4HBO_2(aq)
i. 2H₃BO_3(aq) → B₂O_3(s) + 3H₂O_(l), ∆H⁰ = 14.4 kJ mol^-1
ii. H₃BO_3(aq) → HBO_2(aq) + H₂O_(l), ∆H⁰ = -0.02 kJ mol^-1
iii. H₂B₄O_7(s) → 2B₂O_3(s) + H₂O_(l), ∆H⁰ = 17.3 kJ mol^-1
Answer:
Given equations :
i. 2H₃BO_3(aq) → B₂O_3(s) + 3H₂O_(l), ……….(i)
∆H⁰ = 14.4 kJ mol^-1
ii. H₃BO_3(aq) → HBO_2(aq) + H₂O_(l) ……….(ii)
∆H⁰ = -0.02 kJ mol^-1
iii. H₂B₄O_7(s) → 2B₂O_3(s) + H₂O_(l), ……….(iii)
∆H⁰ = 17.3 kJ mol^-1
Required equation :
(iv) H₂B₄O_7(s) + H₂O_(l) → 4HBO_2(aq) ……. (iv)
\(\Delta H_{4}^{0}=?\)
To obtain eq. (iv) add 4 times equation (ii) and eq.
(iii) and subtract 2 times equation (i).
∴ eq. (iv) = 4 eq. (ii) + eq. (iii) – 2eq. (i)
∴ \(\Delta H_{4}^{0}=4 \Delta H_{2}^{0}+\Delta H_{3}^{0}-2 \Delta H_{1}^{0}\)
= 4(-0.02) + 17.3 – 2(14.4)
= -0.08 + 17.3 – 28.8
= -11.58 kJ
∴ Enthalpy change for the reaction
= ∆_rH⁰ = -11.58 kJ
Ans. ∆_rH⁰ for the given reaction = -11.58 kJ

Question xviii.
Calculate the total heat required (a) to melt 180 g of ice at 0 °C, (b) heat it to 100 °C and then (c) vapourise it at that temperature. Given ∆_fusH_(ice) = 6.01 kJ mol^-1 at 0 °C, ∆_vapH_(H2O) = 40.7 kJ mol^-1 at 100 °C specific heat of water is 4.18 J g^-1 K^-1.
Answer:
Given : Mass of ice = m = 180 g
T₁ = 273 + 0 °C = 273 K
T₂ = 273 + 100 °C = 373 K
∆_fusH_(ice) = ∆_fusH_(H2O)(s) = 6.01 kJ mol^-1
∆_vapH_H2O(l) = 40.7 kJ mol^-1
Specific heat of water = C = 4.18 J g^-1 K^-1
For converting 180 g ice into vapour, ∆ H_Total = ?
Number of moles of H₂O = \(\frac {180}{18}\) = 10 mol
The total process can be represented as,

(i) ∆H₁ = ∆_fusH = 10 mol × 6.01 kJ mol^-1
= 60.1 kJ
(ii) When the temperature of water is raised from 0 °C to 100 °C (i.e., 273 K to 373 K), then
∆ H₂ = m × C × ∆T
= m × C × (T2 – T1)
= 180 g × 4.18 Jg^-1K^-1 × (373 – 273) × 10^-3 kJ = 75.24 kJ
∆ H₃ = ∆_vapH = 10 mol × 40.7 kJ mol^-1 = 407 kJ
Hence total enthalpy change,
∆ H_Total = ∆H₁ + ∆H₂ + ∆H₃
= 60.1 + 75.24 + 407
= 542.34 kJ
Ans. Total heat required = 542.34 kJ

Question xix.
The enthalpy change for the reaction,
C₂H_4(g) + H_2(g) → C₂H_6(g)
is -620 J when 100 ml of ethylene and 100 mL of H₂ react at 1 bar pressure. Calculate the pressure volume type of work and ∆U for the reaction.
Answer:
Given :
\(\begin{aligned}
&\mathrm{C}_{2} \mathrm{H}_{4(\mathrm{~g})}+\mathrm{H}_{2(\mathrm{~g})} \longrightarrow \mathrm{C}_{2} \mathrm{H}_{6(\mathrm{~g})} \\
&100 \mathrm{~mL} \quad 100 \mathrm{ml} \quad 100 \mathrm{ml}
\end{aligned}\)
∆H = – 620 J; V_C2H4 = 100 mL; V_H2 = 100 mL
P_ex= 1 bar; W=?; ∆U = ?
∆V = 100 – (100 + 100) = -100 mL = -0.1 dm³
W = -P_ex(V₂ – V₁)
= -P_ex × ∆V
= -1 × (-0.1)
= 0.1 dm³ bar
= 0.1 × 100 J
= +10 J
∆H = ∆U + P∆V
∴ ∆U = ∆H – P∆V = -620 – (+10) = -610 J
Ans. W = +10 J; ∆U = -610 J

Question xx.
Calculate the work done and comment on whether work is done on or by the system for the decomposition of 2 moles of NH₄NO₃ at 100 °C
NH₄NO_3(s) → N₂O_(g) + 2H₂O_(g)
Answer:
Given : NH₄NO_3(s) → N₂O_(g) + 2H₂O_(g)
n_NH4NO3 = 2 mol; T = 273 + 100 = 373 K
W = ? Comment on work = ?
∆n_reaction = (1 + 2) – 0 = 3 mol
∵ For 1 mol of NH₄NO₃ ∆n_reaction = 3 mol
∴ For 2 mol of NH₄NO₃ ∆n_reaction = 6 mol
Due to 6 moles of gaseous products from 2 mol NH₄NO₃, there is work of expansion, hence work is done by the system.
W = -∆nRT
= – 6 × 8.314 × 373 = -18606 J
= -18.606 kJ
Ans. Work is done by the system.
W= -18.606 kJ

12th Chemistry Digest Chapter 4 Chemical Thermodynamics Intext Questions and Answers

(Textbook page No. 73)

Question 1.
Under what conditions ∆H = ∆U ?
Answer:
(a) ∆H = ∆U + P∆V
when ∆V = 0, ∆H = ∆U
(b) ∆H = ∆U + ∆nRT
when ∆n = 0, ∆H = ∆U

Try this… (Textbook page No. 71)

Question 1.
25 kJ of work is done on the system and it releases 10 kJ of heat. What is ∆U?
Answer:
W = 25 kJ; Q= -10 kJ
∆U = Q + W = -10 + 25
∆U = + 15 kJ

Try this… (Textbook page No. 75)

Question 1.
For KCl, ∆_LH = 699 kJ/mol^-1 and ∆_hydH = -681.8 kJ/mol^-1. What will be its enthalpy of solution?
Answer:
Enthalpy of solution :
∆_solnH = ∆_LH + ∆_hydH
= 699 + (-681.8)
∆_solnH = +17.2 kJ mol^-1

Try this… (Textbook page No. 76)

Question 1.
Given the thermochemical equation,
C₂H_2(g) + \(\frac {5}{2}\) O_2(g) → 2CO_2(g)+ H₂O_(l), ∆_rH⁰ = -1300 kJ
Write thermochemical equations when
i. Coefficients of substances are multiplied by 2.
ii. equation is reversed.
Answer:
(i) 2C₂H_2(g) + 5O_2(g) → 4CO_2(g) + 2H₂O_(l)
∆_rH⁰ = -2 × 1300 kJ
= – 2600 kJ
(ii) 2CO_2(g) + H₂O_(l) → C₂H_2(g) + \(\frac {5}{2}\)O_2(g)
∆_rH⁰ = +1300 KJ

Try this… (Textbook page No. 78)

Question 1.
(i) Write thermochemical equation for complete oxidation of one mole of H_2(g). Standard enthalpy change of the reaction is -286 kJ.
(ii) Is the value -286 kJ, enthalpy of formation or enthalpy of combustion or both? Explain.
Answer:
(i) H_2(g) + \(\frac {1}{2}\)O_2(g) → H₂O_(l) ∆_cH⁰ = -286 KJ mol^-1
(ii) The value -286 kJ is the standard enthalpy of formation of H₂O_(l) or standard enthalpy of combustion of H_2(g).

Question 2.
Write equation for bond enthalpy of Cl-Cl bond in Cl₂ molecule ∆_rH⁰ for dissociation of Cl₂ molecule is 242.7 kJ.
Answer:
Equation for bond enthalpy :
Cl_2(g) → 2Cl_(g) ∆_rH⁰ = 242.7 kJ mol^-1
∴ Bond enthalpy of Cl₂ = 242.7 kJ mol^-1

Try this… (Textbook page No. 82)

Question 1.
State whether ∆S is positive, negative or zero for the following reactions.
i. 2H_2(g) + O_2(g) → 2H₂O_(l)
ii. CaCO_3(s) → CaO_(s) + CO_2(g)
Answer:
(i) 2H_2(g) + O_2(g) → 2H₂O_(l)
Since the system is converted from gaseous state to a liquid state, the disorder is decreased, hence ∆S < O (negative).

(ii) CaCO_3(s) → CaO_(s) + CO_2(g)
Since molecules of solid CaCO₃ break giving gaseous CO₂, disorder is increased hence ∆S > O (positive).

Maharashtra State Board 12th Std Chemistry Textbook Solutions

• Solid State Class 12 Chemistry Textbook Solutions
• Solutions Class 12 Chemistry Textbook Solutions
• Ionic Equilibria Class 12 Chemistry Textbook Solutions
• Chemical Thermodynamics Class 12 Chemistry Textbook Solutions
• Electrochemistry Class 12 Chemistry Textbook Solutions
• Chemical Kinetics Class 12 Chemistry Textbook Solutions
• Elements of Groups 16, 17 and 18 Class 12 Chemistry Textbook Solutions
• Transition and Inner Transition Elements Class 12 Chemistry Textbook Solutions

Ionic Equilibria Class 12 Exercise Question Answers Solutions Maharashtra Board

Balbharti Maharashtra State Board 12th Chemistry Textbook Solutions Chapter 3 Ionic Equilibria Textbook Exercise Questions and Answers.

Class 12 Chemistry Chapter 3 Exercise Solutions Maharashtra Board

Chemistry Class 12 Chapter 3 Exercise Solutions

1. Choose the most correct answer :

Question i.
The pH of 10^-8 M of HCl is
(a) 8
(b) 7
(c) less than 7
(d) greater than 7
Answer:
(c) less than 7

Question ii.
Which of the following solution will have pH value equal to 1.0?
(a) 50 mL of 0.1M HCl + 50mL of 0.1 M NaOH
(b) 60 mL of 0.1M HCl + 40mL of 0.1 M NaOH
(c) 20 mL of 0.1M HCl + 80mL of 0.1 M NaOH
(d) 75 mL of 0.2M HCl + 25mL of 0.2 M NaOH
Answer:
(d) 75 mL of 0.2M HCl + 25mL of 0.2 M NaOH

Question iii.
Which of the following is a buffer solution ?
(a) CH₃COONa + NaCl in water
(b) CH₃COOH + HCl in water
(c) CH₃COOH + CH₃COONa in water
(d) HCl + NH₄Cl in water
Answer:
(c) CH₃COOH + CH₃COONa in water

Question iv.
The solubility product of a sparingly soluble salt AX is 5.2 x 10^-13. Its solubility in mol dm^-3 is
(a) 7.2 × 10^-7
(b) 1.35 × 10^-4
(c) 7.2 × 10^-8
(d) 13.5 × 10^-8
Answer:
(a) 7.2 × 10^-7

Question v.
Blood in human body is highly buffered at pH of
(a) 7.4
(b) 7.0
(c) 6.9
(d) 8.1
Answer:
(a) 7.4

Question vi.
The conjugate base of [Zn(H₂O)₄]²⁺ is
(a) [Zn(H₂O)₄]²⁺ NH3
(b) [Zn(H₂O)₃]²⁺
(c) [Zn(H₂O)₃OH]⁺
(d) [Zn(H₂O)H]³⁺
Answer:
(c) [Zn(H₂O)₃OH]+

Question vii.
For pH > 7 the hydronium ion concentration would be
(a) 10^-7 M
(b) < 10^-7 M
(c) > 10^-7 M
(d) ≥ 10^-7 M
Answer:
(b) < 10^-7 M

2. Answer the following in one sentence :

Question i.
Why cations are Lewis acids ?
Answer:
Since cations are deficient of electrons they accept a pair of electrons, hence they are Lewis acids.

Question ii.
Why is KCl solution neutral to litmus?
Answer:

1. Since KCl is a salt of strong base KOH and strong acid HCl, it does not undergo hydrolysis in its aqueous solution.
2. Due to strong acid and strong base, concentrations [H₃O⁺] = [OH^–] and the solution is neutral.

Question iii.
How are basic buffer solutions prepared?
Answer:

1. Basic buffer solution is prepared by mixing aqueous solutions of a weak base like NH₄OH and its salt of a strong acid like NH₄Cl.
2. A weak base is selected according to the required pH or pOH of the solution and dissociation constant of the weak base.

Question iv.
Dissociation constant of acetic acid is 1.8 × 10^-5. Calculate percent dissociation of acetic acid in 0.01 M solution.
Answer:
Given : K_a = 1.8 x 10^-5; C = 0.01 M
Percent dissociation = ?

∴ Percent dissociation = α × 100
= 4.242 × 10^-2 × 10²
= 4.242%
Percent dissociation = 4.242%

Question v.
Write one property of a buffer solution.
Answer:
Properties (or advantages) of a buffer solution :

• The pH of a buffer solution is maintained appreciably constant.
• By addition of a small amount of an acid or a base pH does not change.
• On dilution with water, pH of the solution doesn’t change.

Question vi.
The pH of a solution is 6.06. Calculate its H⁺ ion concentration.

Question vii.
Calculate the pH of 0.01 M sulphuric acid.
Answer:
Given : C = 0.01 M H₂SO₄, pH = ?
\(\mathrm{H}_{2} \mathrm{SO}_{4(\mathrm{aq})} \longrightarrow 2 \mathrm{H}_{(\mathrm{aq})}^{+}+\mathrm{SO}_{4(\mathrm{aq})}^{2-}\)
∴ [H₃O⁺] = 2 × 0.01 = 0.02 M
PH = -log₁₀ [H₃O⁺]
= -log₁₀ 0.02
= –\((\overline{2} .3010)\)
= 2 – 0.3010
= 1.6990
pH = 1.6990.

Question viii.
The dissociation of H₂S is suppressed in the presence of HCl. Name the phenomenon.
Answer:
The weak dibasic acid H₂S is dissociated as follows :

When HCl is added, it increases the concentration of common ion H₃O⁺.
\(\mathrm{HCl}_{(\mathrm{aq})}+\mathrm{H}_{2} \mathrm{O}_{(\mathrm{l})} \rightarrow \mathrm{H}_{3} \mathrm{O}_{(\mathrm{aq})}^{+}+\mathrm{Cl}_{(\mathrm{aq})}^{-}\)
Hence by Le Chaterlier’s principle, the equilibrium is shifted from right to left, suppressing the dissociation of weak electrolyte H₂S.

Question ix.
Why is it necessary to add H₂SO₄ while preparing the solution of CuSO₄?
Answer:
CuSO₄ is a salt of strong acid H₂SO₄ and weak base Cu(OH)₂. CuSO₄ in aqueous solution undergoes hydrolysis and forms a precipitate of Cu(OH)₂ and solution becomes turbid.
CuSO₄ + 2H₂O ⇌ CU(OH)₂↓ + H₂SO₄
OR
CuSO₄ + 4H₂O ⇌ Cu(OH)₂ + 2H₃O⁺ + \(\mathrm{SO}_{4}^{2-}\)
When H₂SO₄ is added, the hydrolysis equilibrium is shifted to left hand side and Cu(OH)₂ dissolves giving clear solution.

Question x.
Classify the following buffers into different types :
a. CH₃COOH + CH₃COONa
b. NH₄OH + NH₄Cl
c. Sodium benzoate + benzoic acid
d. Cu(OH)₂ + CuCl₂
Answer:
(a) Acidic buffer (CH₃COOH + CH₃COONa)
(b) Basic buffer (NH₄OH + NH₄Cl)
(c) Acidic buffer (Sodium benzoate + benzoic acid)
(d) Basic buffer (Cu(OH)₂ + CuCl₂)
[Note : Cu(OH)₂ being insoluble is not used to prepare a buffer solution.]

3. Answer the following in brief :

Question i.
What are acids and bases according to Arrhenius theory ?
Answer:
According to Arrhenius theory :
Acid : It is a substance which contains hydrogen and on dissolving in water produces hydrogen ions (H⁺) E.g. HCl
\(\mathrm{HCl}_{(\mathrm{aq})} \rightleftharpoons \mathrm{H}_{(\mathrm{aq})}^{+}+\mathrm{Cl}_{(\mathrm{aq})}^{-}\)

Base : It is a substance which contains OH group and on dissolving in water produces hydroxyl ions (OH^–). E.g. NaOH
\(\mathrm{NaOH}_{(\mathrm{aq})} \rightleftharpoons \mathrm{Na}_{(\mathrm{aq})}^{+}+\mathrm{OH}_{(\mathrm{aq})}^{-}\)

Question ii.
What is meant by conjugate acid-base pair?
Answer:
Conjugate acid-base pair : A pair of an acid and a base differing by a proton is called a conjugate acid-base pair.

Question iii.
Label the conjugate acid-base pair in the following reactions
a. HCl + H₂O ⇌ H₃O⁺ + Cl^–
b. \(\mathrm{CO}_{3}^{2-}\) + H₂O ⇌ OH^– + \(\mathrm{HCO}_{3}^{-}\)
Answer:

Question iv.
Write a reaction in which water acts as a base.
Answer:

Since water accepts a proton, it acts as a base.

Question v.
Ammonia serves as a Lewis base whereas AlCl₃ is Lewis acid. Explain.
Answer:

• Since ammonia molecule, NH3 has a lone pair of electrons to donate it acts as a Lewis base.
• AlCl₃ is a molecule with incomplete octet hence it is electron deficient and acts as a Lewis acid.

Question vi.
Acetic acid is 5% ionised in its decimolar solution. Calculate the dissociation constant of acid.
Answer:
Given : C = 0.1 M; Dissociation = 5%, K_a=2 Percent dissociation

Dissociation constant of acid = K_a = 2.63 × 10^-4

Question vii.
Derive the relation pH + pOH = 14.
Answer:
The ionic product of water, Kw is given by,
Kw = [H₃O⁺] × [OH^–]
At 298 K, K_w = 1 × 10^-14
∴ pK_w = -log₁₀K_w = log₁₀ 1 x 10^-14 = 14
∵ [H₃O⁺] × [OH^–] = 1 × 10^-14
Taking logarithm to base 10 of both sides,
log₁₀ [H₃O⁺] + log₁₀ [OH^–] = log₁₀ 1 x 10^-14
Multiplying both the sides by -1,
-log₁₀ [H₃O⁺] -log₁₀ [OH^–] = -log₁₀ 1 x 10^-14
∵ pH = -log₁₀ [H₃O⁺]; pOH = -log₁₀ [OH^–];
pKw = – log₁₀ K_w
∴ pH + pOH = pK_w
OR pH + pOH =14

Question viii.
Aqueous solution of sodium carbonate is alkaline whereas aqueous solution of ammonium chloride is acidic. Explain.
Answer:
(A) (i) Sodium carbonate is a salt of weak acid and strong base.
(ii) In aqueous solution it undergoes hydrolysis.

(iii) Strong base dissociates completely while weak acid dissociates partially since [OH^–] > [H₃O⁺], the solution is basic.

(B) (i) Ammonium chloride is a salt of strong acid and weak base.
(ii) In aqueous solution it undergoes hydrolysis

(iii) Since [H⁺] or [H₃O⁺ ] > [OH^–] the solution is acidic.

Question ix.
pH of a weak monobasic acid is 3.2 in its 0.02 M solution. Calculate its dissociation constant.
Answer:
Given : pH = 3.2; C = 0.02 M; K_a = ?
pH = -log₁₀ [H⁺]
∴ [H⁺] = Antilog – pH
= Antilog – 3.2
= Antilog \(\overline{4} .8\)
= 6.31 × 10^-4M

K_a = cα²
= 0.02 × (0.0315)²
= 1.984 × 10^-5
Dissociation constant = K_a = 1.984 × 10^-5

Question x.
In NaOH solution [OH^–] is 2.87 × 10^-4. Calculate the pH of solution.
Answer:
Given : [OH^–] = 2.87 × 10^-4 M, pH = ?
pOH = -log₁₀ [OH^–]
= -log₁₀ 2.87 × 10^-4
= –\((\overline{4} .4579)\)
= (4 – 0.4579)
= 3.5421
∵ pH + pOH = 14
∴ pH = 14 – pOH = 14 – 3.5421 = 10.4579
pH = 10.4579.

4. Answer the following :

Question i.
Define degree of dissociation. Derive Ostwald’s dilution law for the CH₃COOH.
Answer:
(A) Degree of dissociation :
It is defined as a fraction of total number of moles of an electrolyte that dissociate into its ions at equilibrium.
It is denoted by a and represented by,
α = \(\frac{\text { number of moles dissociated }}{\text { total number of moles of an electrolyte }}\)
Or α = \(\frac{\text { Per cent dissociation }}{100}\)
∴ Per cent dissociation = α × 100

(B) Consider V dm³ of a solution containing one mole of CH₃COOH. Then the concentration of acid is, C = \(\frac{1}{V}\) mol dm³. Let α be the degree of dissociation


This is Ostwald’s dilution law.

Question ii.
Define pH and pOH. Derive relationship between pH and pOH.
Answer:
(1) pH : The negative logarithm, to the base 10, of the molar concentration of hydrogen ions, H⁺ is known as the pH of a solution.
pH = -log₁₀ [H⁺]

(2) pOH : The negative logarithm, to the base 10, of the molar concentration of hydroxyl ions, OH^– is known as the pOH of a solution.
pOH = -log₁₀ [OH^–]

Relationship between pH and pOH:
The ionic product of water, Kw is given by,
K_w = [H₃O⁺] × [OH^–]
At 298 K, K_w = 1 × 10^-14
∴ pK_w = -log₁₀K_w = log₁₀ 1 x 10^-14 = 14
∵ [H₃O⁺] × [OH^–] = 1 × 10^-14
Taking logarithm to base 10 of both sides,
log₁₀ [H₃O⁺] + log₁₀ [OH^–] = log₁₀ 1 x 10^-14
Multiplying both the sides by -1,
-log₁₀ [H₃O⁺] – log₁₀ [OH^–] = -log₁₀ 1 x 10^-14
∵ pH = -log₁₀ [H₃O⁺]; pOH = -log₁₀ [OH^–];
pK_w = – log₁₀ K_w
∴ pH + pOH = pK_w
OR pH + pOH =14

Question iii.
What is meant by hydrolysis ? A solution of CH₃COONH₄ is neutral. why ?
Answer:
Hydrolysis : A reaction in which the cations or anions or both the ions of a salt react with water to produce acidity or basicity or sometimes neutrality is called hydrolysis.

A salt of weak acid and weak base for which K_a = K_b:
Consider hydrolysis of CH₃COONH₄.

Since K_a = K_b, the weak acid CH₃COOH and weak base NH₄OH dissociate to the same extent, hence, [H₃O⁺] = [OH^–] and the solution reacts neutral after hydrolysis.

Question iv.
Dissociation of HCN is suppressed by the addition of HCl. Explain.
Answer:
The weak acid HCN is dissociated as follows :
\(\mathrm{HCN}_{(\mathrm{aq})}+\mathrm{H}_{2} \mathrm{O}_{(\mathrm{l})} \rightleftharpoons \mathrm{H}_{3} \mathrm{O}_{(\mathrm{aq})}^{+}+\mathrm{CN}_{(\mathrm{aq})}^{-}\)
The dissociation constant K_a is represented as,
K_a = \(\frac{\left[\mathrm{H}_{3} \mathrm{O}^{+}\right] \times\left[\mathrm{CN}^{-}\right]}{[\mathrm{HCN}]}\)
When HCl is added, it increases the concentration of H₃O⁺, hence in order to keep the ratio constant, then by Le Chatelier’s principle, the equilibrium is shifted from right to left, suppressing the dissociation of HCN.

Question v.
Derive the relationship between degree of dissociation and dissociation constant in weak electrolytes.
Answer:
Expression of Ostwald’s dilution law in the case of a weak electrolyte : Consider the dissociation of a weak electrolyte BA. Let V dm³ of a solution contain one mole of the electrolyte. Then the concentration of a solution is, C = \(\frac{1}{V}\)mol dm^-3. Let α be the degree of dissociation of the electrolyte.

Applying the law of mass action to this dissociation equilibrium, we have,

As the electrolyte is weak, α is very small as compared to unity, ∴ (1 – α) ≈ 1.

This is the expression of Ostwald’s dilution law. Thus, the degree of dissociation of a weak electrolyte is directly proportional to the square root of the volume of the solution containing 1 mole of an electrolyte.

Question vi.
Sulfides of cation of group II are precipitated in acidic solution (H₂S + HCl) whereas sulfides of cations of group IIIB are precipitated in ammoniacal solution of H₂S. Comment on the relative values of solubility product of sulfides of these.
Answer:
(1) In qualitative analysis, the cations of group II are precipitated as sulphides, namely HgS, CuS, PbS, etc., while cations of group IIIB are precipitated as sulphides, namely, CoS, NiS, ZnS.

(2) The sulphides of group II have extremely low solubility product (K_sp) about 10^-29 to 10^-53 while the sulphides of group IIIB have slightly higher K_sp values about 10^-20 to 10^-23.

(3) In group II, sulphides are precipitated by adding H₂S in acidic solution while in IIIB group they are precipitated in a basic solution like ammonical solution.

(4) In acidic medium due to common ion H⁺, H₂S is dissociated to very less extent but gives sufficient S^2- ion to exceed solubility product of group II sulphides of cations and precipitate them.
\(\mathrm{HCl}_{(\mathrm{aq})} \longrightarrow \mathrm{H}_{(\mathrm{aq})}^{+}+\mathrm{Cl}_{(\mathrm{aq})}^{-} ; \mathrm{H}_{2} \mathrm{~S}_{(\mathrm{aq})} \rightleftharpoons 2 \mathrm{H}_{(\mathrm{aq})}^{+}+\mathrm{S}_{(\mathrm{aq})}^{2-}\)

(5) In basic medium, H⁺ from H₂S are removed by OH^– in solution, or by NH₄OH, increasing the dissociation of H₂S and concentration of S^2-, so that IP > K_sp.

(6) Therefore group II cations are precipitated in an acidic medium while cations of group IIIB are precipitated in ammonical solution.

Question vii.
Solubility of a sparingly soluble salt get affected in presence of a soluble salt having one common ion. Explain.
Answer:
Consider the solubility equilibrium of a sparingly soluble salt, AgCl.
\(\mathrm{AgCl}_{(\mathrm{s})} \rightleftharpoons \mathrm{Ag}_{(\mathrm{aq})}^{+}+\mathrm{Cl}_{(\mathrm{aq})}^{-}\)
The solubility product, K_sp is given by,
K_sp = [Ag⁺] × [Cl^–]
Consider addition of a strong electrolyte AgNO₃ with a common ion Ag⁺.
\(\mathrm{AgNO}_{3(\mathrm{aq})} \longrightarrow \mathrm{Ag}_{(\mathrm{aq})}^{+}+\mathrm{NO}_{3(\mathrm{aq})}^{-}\)
The concentration Ag⁺ in the solution is increased, hence by Le Chatelier’s principle the equilibrium of AgCl is shifted to left hand side since the value of K_sp is constant.
Thus in the presence of a common ion, the solubility of a sparingly soluble salt is suppressed.

Question viii.
The pH of rain water collected in a certain region of Maharashtra on particular day was 5.1. Calculate the H₃O⁺ ion concentration of the rain water and its percent dissociation.
Answer:
Given : pH = 5.1, [H₃O⁺] = ?
PH = -log₁₀ [H₃O⁺]
∴ log₁₀ [H₃O⁺] = -pH
∴ [H₃O⁺] = Antilog – pH
= Antilog – 5.1
= Antilog \(\overline{6} .9\)
= 7.943 × 10^-6 M
(H₃O⁺ in rainwater is due to dissolved gases, CO₂, SO₂, etc. forming acids which dissociate giving H₃O⁺ and acidity to rainwater.)
[H₃O⁺] = 7.943 × 10^-4 M

Question ix.
Explain the relation between ionic product and solubility product to predict whether a precipitate will form when two solutions are mixed?
Answer:
If ionic product and solubility product are indicated by IP and K_sp respectively then,
(I) When IP = K_sp, the solution is saturated.
(II) When IP > K_sp, the solution is supersaturated and hence precipitation will occur, when two solutions are mixed.
(Ill) When IP < K_sp, the solution is unsaturated and precipitation will not occur, when two solutions are mixed.

12th Chemistry Digest Chapter 3 Ionic Equilibria Intext Questions and Answers

Use your brain power (Textbook Page No. 47)

Question 1.
Which of the following is a strong electrolyte ?
HF, AgCl, CuSO₄, CH₃COONH₄, H₃PO₄.
Answer:
CH₃COONH₄ is a strong electrolyte since in aqueous solution it dissociates completely. Sparingly soluble salts AgCl, CuSO₄ are also strong electrolytes.

Use your brain power (Textbook Page No. 49)

Question 1.
All Bronsted bases are also Lewis bases, but all Bronsted acids are not Lewis acids. Explain.
Answer:
NH₃ is a Bronsted base since it can accept a proton while it is also a Lewis base since it has a lone pair of electrons to donate.

(2) HCl is a Bronsted acid since it can donate a proton but it is not a Lewis acid since it can’t accept a pair of electrons.

Use your brain power (Textbook Page No. 53)

Question 1.
Suppose that pH of monobasic and dibasic acid is the same. Does this mean that the molar concentrations of both acids are identical ?
Answer:
Even if monobasic acid and dibasic acid give same pH, their molar concentrations are different. One mole of monobasic acid like HCl gives 1 mol of H⁺ while one mole of dibasic acid gives 2 mol of H⁺ in solution. Hence the concentration of dibasic acid will be half of the concentration of monobasic acid. For example, for same pH. [Monobasic acid] = [Dibasic acid]/2

Question 2.
How does pH of pure water vary with temperature ? Explain.
Answer:
Since the increase in temperature, increases the dissociation of water, its pH decreases.

Can you tell ? (Textbook Page No. 54)

Question 1.
Why (i) an aqueous solution of NH₄Cl is acidic.
(ii) while that of HCOOK basic ?
Answer:
(i) (i) Ammonium chloride is a salt of strong acid and weak base.
(ii) In aqueous solution it undergoes hydrolysis

(iii) Since [H⁺] or [H₃O⁺] > [OH^–] the solution is acidic.

(ii) HCOOK is a salt of weak acid HCOOH and strong base KOH. In aqueous solution it undergoes hydrolysis giving weak acid and strong base KOH which dissociates completely,

∴ [OH^–] > [H₃O⁺], and the solution reacts basic.

Can you think ? (Textbook Page No. 56)

Question 1.
Home made jams and jellies without any added chemical preservative additives spoil in a few days whereas commercial jams and jellies have a long shelf life. Explain. What role does added sodium benzoate play ?
Answer:
Sodium benzoate added to jams and jellies in commercial products maintains the pH constant and acts as a preservative. Hence jams and jellies are not spoiled for a very long time unlike homemade products.

Can you tell ? (Textbook Page No. 56)

Question 1.
It is enough to add a few mL of a buffer solution to maintain its pH. Which property of buffer is used here ?
Answer:
The important property of reserve acidity and reserve basicity of a buffer solution is used to maintain constant pH. Weak acid or weak base along with ions (cations or anions) from salt react with excess of added acid (H⁺) or base [OH^–] and maintain pH constant.

Use your brain power (Textbook Page No. 59)

Question 1.
What is the relationship between molar solubility and solubility product for salts given below : (i) Ag₂CrO₄ (ii) Ca₃(PO₄)₂ (iii) Cr(OH)₃.
Answer:

Can you tell ? (Textbook Page No. 60)

Question 1.
How is the ionization of NH₄OH suppressed by addition of NH₄Cl to the solution of NH₄OH ?
Answer:
Ionisation of NH₄OH is represented as follows :
\(\mathrm{NH}_{4} \mathrm{OH}_{(\mathrm{aq})} \rightleftharpoons \mathrm{NH}_{4(\mathrm{aq})}^{+}+\mathrm{OH}_{(\mathrm{aq})}^{-}\)
It has ionisation constant,
K_b = \(\frac{\left[\mathrm{NH}^{4+}\right] \times\left[\mathrm{OH}^{-}\right]}{\left[\mathrm{NH}_{4} \mathrm{OH}\right]}\)
K_b has constant value at constant temperature. When strong electrolyte NH₄Cl is added to its solution, it dissociates completely.
\(\mathrm{NH}_{4} \mathrm{Cl}_{(\mathrm{aq})} \longrightarrow \mathrm{NH}_{4(\mathrm{aq})}^{+}+\mathrm{Cl}_{(\mathrm{aq})}^{-}\)
Due to common ion \(\mathrm{NH}_{4}^{+}\), by Le Chatelier’s principle, the equilibrium is shifted from right to left, suppressing the ionisation of NH₄OH.

Maharashtra State Board 12th Std Chemistry Textbook Solutions

• Solid State Class 12 Chemistry Textbook Solutions
• Solutions Class 12 Chemistry Textbook Solutions
• Ionic Equilibria Class 12 Chemistry Textbook Solutions
• Chemical Thermodynamics Class 12 Chemistry Textbook Solutions
• Electrochemistry Class 12 Chemistry Textbook Solutions
• Chemical Kinetics Class 12 Chemistry Textbook Solutions
• Elements of Groups 16, 17 and 18 Class 12 Chemistry Textbook Solutions
• Transition and Inner Transition Elements Class 12 Chemistry Textbook Solutions

Solutions Class 12 Exercise Question Answers Solutions Maharashtra Board

Balbharti Maharashtra State Board 12th Chemistry Textbook Solutions Chapter 2 Solutions Textbook Exercise Questions and Answers.

Class 12 Chemistry Chapter 2 Exercise Solutions Maharashtra Board

Chemistry Class 12 Chapter 2 Exercise Solutions

1. Choose the most correct answer.

Question i.
The vapour pressure of a solution containing 2 moles of a solute in 2 moles of water (vapour pressure of pure water = 24 mm Hg) is
(a) 24 mm Hg
(b) 32 mm Hg
(c) 48 mm Hg
(d) 12 mm Hg
Answer:
(d) 12 mm Hg

Question ii.
The colligative property of a solution is
(a) vapour pressure
(b) boiling point
(c) osmotic pressure
(d) freezing point
Answer:
(c) osmotic pressure

Question iii.
In calculating osmotic pressure the concentration of solute is expressed in
(a) molarity
(b) molality
(c) mole fraction
(d) mass per cent
Answer:
(a) molarity

Question iv.
Ebullioscopic constant is the boiling point elevation when the concentration of solution is
(a) 1 m
(b) 1 M
(c) 1 mass%
(d) 1 mole fraction of solute
Answer:
(a) 1 m

Question v.
Cryoscopic constant depends on
(a) nature of solvent
(b) nature of solute
(c) nature of solution
(d) number of solvent molecules
Answer:
(a) nature of solvent

Question vi.
Identify the correct statement
(a) vapour pressure of solution is higher than that of pure solvent.
(b) boiling point of solvent is lower than that of solution
(c) osmotic pressure of solution is lower than that of solvent
(d) osmosis is a colligative property.
Answer:
(b) boiling point of solvent is lower than that of solution

Question vii.
A living cell contains a solution which is isotonic with 0.3 M sugar solution. What osmotic pressure develops when the cell is placed in 0.1 M KCl solution at body temperature ?
(a) 5.08 atm
(b) 2.54 atm
(c) 4.92 atm
(d) 2.46 atm
Answer:
(c) 4.92 atm

Question viii.
The osmotic pressure of blood is 7.65 atm at 310 K. An aqueous solution of glucose isotonic with blood has the percentage (by volume)
(a) 5.41%
(b) 3.54%
(c) 4.53%
(d) 53.4%
Answer:
(a) 5.41%

Question ix.
Vapour pressure of a solution is
(a) directly proportional to the mole fraction of the solute
(b) inversely proportional to the mole fraction of the solute
(c) inversely proportional to the mole fraction of the solvent
(d) directly proportional to the mole fraction of the solvent
Answer:
(d) directly proportional to the mole fraction of the solvent

Question x.
Pressure cooker reduces cooking time for food because
(a) boiling point of water involved in cooking is increased
(b) heat is more evenly distributed in the cooking space
(c) the higher pressure inside the cooker crushes the food material
(d) cooking involves chemical changes helped by a rise in temperature
Answer:
(a) boiling point of water involved in cooking is increased

Question xi.
Henry’s law constant for a gas CH₃Br is 0.159 mol dm^-3 atm at 250°C. What is the solubility of CH₃Br in water at 25 °C and a partial pressure of 0.164 atm?
(a) 0.0159 mol L^-1
(b) 0.164 mol L^-1
(c) 0.026 M
(d) 0.042 M
Answer:
(c) 0.026 M

Question xii.
Which of the following statement is NOT correct for 0.1 M urea solution and 0.05 M sucrose solution ?
(a) osmotic pressure exhibited by urea solution is higher than that exhibited by sucrose solution
(b) urea solution is hypertonic to sucrose solution
(c) they are isotonic solutions
(d) sucrose solution is hypotonic to urea solution
Answer:
(c) they are isotonic solutions

2. Answer the following in one or two sentences

Question i.
What is osmotic pressure ?
Answer:
(1) Definition : The osmotic pressure is defined as the excess mechanical pressure required to be applied to a solution separated by a semipermeable membrane from pure solvent or a dilute solution to prevent the osmosis or free passage of the solvent molecules at a given temperature. The osmotic pressure is a colligative property.

Osmosis and osmotic pressure

(2) Explanation : Consider an inverted thistle funnel on the mouth of which a semipermeable membrane is firmly fastened. It is filled with the experimental solution and immersed in a solvent like water. As a result, solvent molecules pass through the membrane into the solution in the funnel causing rising of level in the arm of thistle funnel. This increases the hydrostatic pressure. At a certain stage this rising level stops indicating an equilibrium between the rates of flow of solvent molecules from solvent to solution and from solution to solvent. The hydrostatic pressure at this stage represents osmotic pressure of the solution in the thistle funnel.

Question ii.
A solution concentration is expressed in molarity and not in molality while considering osmotic pressure. Why ?
Answer:

1. While calculating osmotic pressure by equation, π = CRT, the concentration is expressed in molarity but not in molality.
2. This is because the measurements of osmotic pressure are made at a certain constant temperature.
3. Molarity depends upon temperature but molality is independent of temperature.
4. Hence in osmotic pressure measurements, concentration is expressed in molarity.

Question iii.
Write the equation relating boiling point elevation to the concentration of solution.
Answer:
The elevation in the boiling point of a solution is directly proportional to the molal concentration (expressed in mol kg^-1) of the solution.
Hence, if ΔT_b is the elevation in the boiling point of a solution of molal concentration m then,
ΔT_b ∝ m
∴ ΔT_b = K_b m
where K_b is a proportionality constant.
If m = 1 molal,
ΔT_b = K_b
K_b is called the ebullioscopic constant or molal elevation constant. K_b is characteristic of the solvent.

Question iv.
A 0.1 m solution of K₂SO₄ in water has freezing point of -0.43 °C. What is the value of van’t Hoff factor if K_f for water is 1.86 K kg mol^-1?
Answer:
Given : m = 0.1 m, ΔT_f = 0 – (-0.43) = 0.43 °C
K_f = 1.86 K kg mol^-1, i = ?
ΔT_f = i × K_f × m
∴ i = \(\frac{\Delta T_{\mathrm{f}}}{K_{\mathrm{f}} \times m}=\frac{0.43}{1.86 \times 0.1}\) = 2.312
van’t Hoff factor = i = 2.312

Question v.
What is van’t Hoff factor?
Answer:
Definition of the van’t Hoff factor, i : It is defined as a ratio of the observed colligative property of the solution to the theoretically calculated colligative property of the solution without considering molecular change.

The van’t Hoff factor can be represented as,

This colligative property may be the lowering of vapour pressure of a solution, the osmotic pressure, the elevation in the boiling point or the depression in the freezing point of the solution. Hence,

• When the solute neither undergoes dissociation or association in the solution, then, i = 1
• When the solute undergoes dissociation in the solution, then, i > 1
• When the solute undergoes association in the solution, then i < 1

From the value of the van’t Hoff factor, the degree of dissociation of electrolytes, degree of association of nonelectrolytes can be obtained.

van’t Hoff factor gives the important information about the solute molecules in the solution and chemical bonding in them.

Question vi.
How is van’t Hoff factor related to degree of ionization?
Answer:
Consider 1 dm³ of a solution containing m moles of an electrolyte AxBy. The electrolyte on dissociation gives x number of A^y+ ions and y number of B^x- ions. Let α be the degree of dissociation.

At equilibrium,
AxBy ⇌ xA^y+ + yB^x-
For 1 mole of electrolyte : 1 – α,  xα,  yα
and For ‘m’ moles of an electrolyte : m(1 – α), mxα, myα are the number of particles.
Total number of moles at equilibrium, will be,
Total moles = m(1 – α) + mxα + myα
= m[(1 – α) + xα + yα]
= m[1 + xα + yα – α]
= m[1 + α(x + y – 1)]

The van’t Hoff factor i will be,

If total number of ions from one mole of electrolyte is denoted by n, then (x + y) = n
∴ i = 1 + α(n – 1)
∴ α(n – 1) = i – 1
∴ α = \(\frac{i-1}{n-1}\) ……(1)
This is a relation between van’t Hoff factor i and degree of dissociation of an electrolyte.

Question vii.
Which of the following solutions will have higher freezing point depression and why ?
a. 0.1 m NaCl b. 0.05 m Al₂(SO₄)₃
Answer:
(1) Freezing point depression is a colligative property, hence depends on the number of particles in the solution.
(2) More the number of particles in the solution, higher is the depression in freezing point.
(3) The number of particles (ions) from electrolytes are,

(4) Therefore Al₂(SO₄)₃ solution will have higher freezing point depression.

Question viii.
State Raoult’s law for a solution containing a nonvolatile solute.
Answer:
Statement of Raoult’s law : The law states that the vapour pressure of a solvent over the solution of a nonvolatile solute is equal to the vapour pressure of the pure solvent multiplied by mole fraction of the solvent at constant temperature.

Question ix.
What is the effect on the boiling point of water if 1 mole of methyl alcohol is added to 1 dm³ of water? Why?
Answer:

• The boiling point of water (or any liquid) depends on its vapour pressure.
• Higher the vapour pressure, lower is the boiling point.
• When 1 mole of volatile methyl alcohol is added to 1 dm³ of water, its vapour pressure is increased decreasing the boiling point of water.

Question x.
Which of the four colligative properties is most often used for molecular mass determination? Why?
Answer:

1. Since osmotic pressure has large values, it can be measured more precisely.
2. The osmotic pressure can be measured at a suitable constant temperature.
3. The molecular masses can be measured more accurately.
4. Therefore, it is more useful to determine molecular masses of expensive substances by osmotic pressure.

3. Answer the following.

Question i.
How vapour pressure lowering is related to a rise in boiling point of solution?
Answer:
(1) The boiling point of a liquid is the temperature at which the vapour pressure of the liquid becomes equal to the external pressure, generally 1 atm (101.3 × 10³ Nm^-2).

(2) When a liquid is heated, its vapour pressure rises till it becomes equal to the external pressure.
If the liquid has a low vapour pressure, it has a higher boiling point.

Vapour pressure curve showing elevation in boiling point

(3) When a nonvolatile solute is added to a solvent, its vapour pressure decreases, hence the boiling point increases.
This is explained by graphical representation of the vapour pressure and the boiling point of the pure solvent and the solution.

If T₀ and T are the boiling points of a pure solvent and a solution, then the elevation in the boiling point is given by,
ΔT_b = T – T₀
The curve AB, represents the variation in the vapour pressure of a pure solvent with temperature while curve CD represents the variation in the vapour pressure of the solution.

(4) This elevation in the boiling point is proportional to the lowering of the vapour pressure, i.e., P₀ – P, where P₀ and P are the vapour pressures of the pure solvent and the solution.
[ΔT_b ∝ (P₀ – P) or ΔT_b ∝ ΔP]

Question ii.
What are isotonic and hypertonic solutions?
Answer:
(1) Isotonic solutions : The solutions having the same osmotic pressure at a given temperature are called isotonic solutions.

Explanation : If two solutions of substances A and B contain n_A and n_B moles dissolved in volume V (in dm³) of the solutions, then their concentrations are,
C_A = \(\frac{n_{\mathrm{A}}}{V}\) (in mol dm^-3) and
C_B = \(\frac{n_{\mathrm{B}}}{V}\) (in mol dm^-3)

If the absolute temperature of both the solutions is T, then by the van’t Hoff equation,
π_A = C_ART and π_B = C_BRT, where π_A and π_B are their osmotic pressures.
For the isotonic solutions,
π_A = π_B
∴ C_A = C_B
∴ \(\frac{n_{\mathrm{A}}}{V}=\frac{n_{\mathrm{B}}}{V}\)
∴ n_A = n_B
Hence, equal volumes of the isotonic solutions at the same temperature will contain equal number of moles (hence, equal number of molecules) of the substances.

(2) Hypertonic solutions : When two solutions have different osmotic pressures, then the solution having higher osmotic pressure is said to be a hypertonic solution with respect to the other solution.

Explanation : Consider two solutions of substances A and B having osmotic pressures π_A and π_B. If π_B is greater than π_A, then the solution B is a hypertonic solution with respect to the solution A.
Hence, if C_A and C_B are their concentrations, then C_B > C_A. Hence, for equal volume of the solutions, n_B > n_A.

Question iii.
A solvent and its solution containing a nonvolatile solute are separated by a semipermable membrane. Does the flow of solvent occur in both directions? Comment giving reason.
Answer:

1. When a solvent and a solution containing a non-volatile solute are separated by a semipermeable membrane, there arises a flow of solvent molecules from solvent to solution as well as from solution to solvent.
2. Due to higher vapour pressure of solvent than solution, the rate of flow of solvent molecules from solvent to solution is higher.
3. As more and more solvent passes into solution due to osmosis, the solvent content increases, and the rate of backward flow increases.
4. At a certain stage an equilibrium is reached where both the opposing rates become equal attaining an equilibrium.

Question iv.
The osmotic pressure of CaCl₂ and urea solutions of the same concentration at the same temperature are respectively 0.605 atm and 0.245 atm. Calculate van’t Hoff factor for CaCl₂.
Answer:
Given : π_Cacl2 = 0.605 atm;
π_Urea = 0.245 atm
For urea solution, van’t Hoff factor, i = 1
π_Cacl2 = i × (CRT)_Cacl2
π_Urea = (CRT)_Urea

van’t Hoff factor = i = 2.47

Question v.
Explain reverse osmosis.
Answer:
Reverse osmosis : The phenomenon of the passage of solvent like water under high pressure from the concentrated aqueous solution like seawater into pure water through a semipermeable membrane is called reverse osmosis.

The osmotic pressure of seawater is about 30 atmospheres. Hence when pressure more than 30 atmospheres is applied on the solution side, regular osmosis stops and reverse osmosis starts. Hence pure water from seawater enters the other side of pure water.

Purification of seawater by reverse osmosis

For this purpose of suitable semipermeable membrane is required which can withstand high pressure conditions over a long period.
This method is used successfully in Florida since 1981 producing more than 10 million litres of pure water per day.

Question vi.
How molar mass of a solute is determined by osmotic pressure measurement?
Answer:
Consider V dm³ (litres) of a solution containing W₂ mass of a solute of molar mass M₂ at a temperature T.
Number of moles of solute, n₂ = \(\frac{W_{2}}{M_{2}}\)
The osmotic pressure π is given by,
π = \(\frac{W_{2} R T}{M_{2} V}\)
∴ M₂ = \(\frac{W_{2} R T}{\pi V}\)
By measuring osmotic pressure of a solution, the molar mass of a solute can be calculated.
Since osmotic pressure can be measured more precisely, it is widely used to measure molar masses of the substances.

Question vii.
Why vapour pressure of a solvent is lowered by dissolving a nonvolatile solute into it?
Answer:
Lowering of vapour pressure of a solution :
When a nonvolatile solute is added to a pure solvent, the surface area is covered by the solute molecule decreasing the rate of evaporation, hence its vapour pressure decreases. This decrease in vapour pressure is called lowering of vapour pressure.

If P₀ is the vapour pressure of a pure solvent (liquid) and P is the vapour pressure of the solution, where P < P₀, then, (P₀ – P) is the lowering of the vapour pressure.

Question viii.
Using Raoult’s law, how will you show that ∆P = \(\boldsymbol{P}_{1}^{0}\)x₂ ? Where x₂ is the mole fraction of solute in the solution and \(\boldsymbol{P}_{1}^{0}\) vapour pressure of pure solvent.
Answer:
If x₁ and x₂ are the mole fractions of solvent and solute respectively, then
x₁ + x₂
By Raoult’s law,
P = x₁ × P₀
where P⁰ is the vapour pressure of a pure solvent and P is the vapour pressure of the solution at given temperature.

Question ix.
While considering boiling point elevation and freezing point depression a solution concentration is expressed in molality and not in molarity. Why?
Answer:

• Boiling point elevation and freezing point depression involve temperature changes, (ΔT_b and ΔT_f).
• Since molarity depends on temperature but molality is independent of temperature we use molality and not molarity in considering boiling point elevation and freezing point depression.

Question 4.
Derive the relationship between degree of dissociation of an electrolyte and van’t Hoff factor.
Answer:
Consider 1 dm³ of a solution containing m moles of an electrolyte AxBy. The electrolyte on dissociation gives number of A^y+ ions and y number of B^x- ions. Let α be the degree of dissociation.

At equilibrium,
AxBy ⇌ xA^y+ + yB^x-
For 1 mole of electrolyte : 1 – α, xα, yα and
For ‘m’ moles of an electrolyte : m(1 – α), mxα, myα are the number of particles.
Total number of moles at equilibrium, will be,
Total moles = m(1 – α) + mxα + myα
= m[(1 – α) + xα + yα]
= m[1 – xα + yα – α]
= m[1 + α(x + y – 1)]
The van’t Hoff factor i will be,

If total number of ions from one mole of electrolyte is denoted by n, then (x + y) = n
∴ i = 1 + α(n – 1)
∴ α(n – 1) = i – 1
∴ α = \(\frac{i-1}{n-1}\) ……..(1)
This is a relation between van’t Hoff factor i and degree of dissociation of an electrolyte.

Question 5.
What is effect of temperature on solubility of solids in water? Give examples.
Answer:
The solubility of a solid solute depends upon temperature.

Variation of solubilities of some ionic solids with temperature

• Generally rise in temperature increases the solubility. This is due to expansion of holes or empty spaces in the liquid solvent. Generally 10 °C rise in temperature, increases the solubility of solids two fold.
• Dissolution process may be endothermic or exothermic.
• The solubility of the substances like NaBr, NaCl, KCl, etc. changes slightly with the increase in temperature.
• The solubility of the salts like NaNO₃, KNO₃, KBr, etc. increases appreciably with the increase in temperature.
• The solubility of Na₂SO₄ first increases and after 30 °C decreases with the increase in temperature.

This variation in solubility with temperature can be used to separate the salts from the mixture by fractional crystallisation.

Question 6.
Obtain the relationship between freezing point depression of a solution containing nonvolatile nonelectrolyte and its molar mass.
Answer:
The freezing point depression, ΔT_f of a solution is directly proportional to molality (m) of the solution.
∴ ΔT_f ∝ m
∴ ΔT_f = K_f m
where Kf is a molal depression constant.
The molality of a solution is given by,

If W₁ grams of a solvent contain W₂ grams of a solute of the molar mass M₂, then the molality m of the solution is given by,

If the weights are expressed in kg then,
ΔT_f = K_f × \(\frac{W_{2}}{W_{1} M_{2}}\)
The unit of K_f is K kg mol^-1
Hence, from the measurement of the depression in the freezing point of the solution, the molar mass of the substance can be determined.

Question 7.
Explain with diagram the boiling point elevation in terms of vapour pressure lowering.
Answer:
(1) The boiling point of a liquid is the temperature at which the vapour pressure of the liquid becomes equal to the external pressure, generally 1 atm (101.3 × 10³ Nm^-2).

(2) When a liquid is heated, its vapour pressure rises till it becomes equal to the external pressure.
If the liquid has a low vapour pressure, it has a higher boiling point.

Vapour pressure curve showing elevation in boiling point

(3) When a nonvolatile solute is added to a solvent, its vapour pressure decreases, hence the boiling point increases.
This is explained by graphical representation of the vapour pressure and the boiling point of the pure solvent and the solution.

If T₀ and T are the boiling points of a pure solvent and a solution, then the elevation in the boiling point is given by,
ΔT_b = T – T₀
The curve AB, represents the variation in the vapour pressure of a pure solvent with temperature while curve CD represents the variation in the vapour pressure of the solution.

(4) This elevation in the boiling point is proportional to the lowering of the vapour pressure, i.e., P₀ – P, where P₀ and P are the vapour pressures of the pure solvent and the solution.
[ΔT_b ∝ (P₀ – P) or ΔT_b ∝ ΔP]

Question 8.
Fish generally needs O₂ concentration in water at least 3.8 mg/L for survival. What partial pressure of O₂ above the water is needed for the survival of fish? Given the solubility of O₂ in water at 0 °C and 1 atm partial pressure is 2.2 × 10^-3 mol/L (0.054 atm)
Answer:
Given : Required concentration of O₂
= 3.8 mg/L
= \(\frac{3.8 \times 10^{-3}}{32} \mathrm{~mol} \mathrm{~L}^{-1}\)
Solubility of O₂ = 2.2 × 10^-3 mol L^-1
P = 1 atm
Partial pressure of O₂ needed = Po₂ = ?

Pressure needed = Po₂ = 0.05397 atm.

Question 9.
The vapour pressure of water at 20 °C is 17 mm Hg. What is the vapour pressure of solution containing 2.8 g urea in 50 g of water? (16.17 mm Hg)
Answer:
Given : Vapour pressure of pure solvent (water) = P0
= 17 mm Hg
Weight of solvent = W₁ = 50 g
Weight of solute (urea) = 2.8 g
Molecular weight of a solvent = M₁ = 18
Molecular weight of a solute (urea) = M₂
= 60 g mol^-1
\(\frac{P_{0}-P}{P_{0}}=\frac{W_{2} \times M_{1}}{W_{1} \times M_{2}}\)
∴ \(\frac{17-P}{17}=\frac{2.8 \times 18}{50 \times 60}\) = 0.0168
∴ 17 – P = 17 × 0.0168
17 – P = 0.2856
∴ P= 17 – 0.2856
= 16.7144 mm Hg
Vapour pressure of solution = 16.7144 mm Hg

Question 10.
A 5% aqueous solution (by mass) of cane sugar (molar mass 342 g/mol) has freezing point of 271K. Calculate the freezing point of 5% aqueous glucose solution.
Answer:
Given : W₂ = 5 g cane sugar; W₁ = 100 – 5 = 95 g
M₂ = 342 g mol^-1; T_f1 = 271 K;
ΔT_f1 = 273 – 271 = 2 K; T_f = ?
W₂ = 5 g glucose, W’₁ = 100 – 5 = 95 g,
M’₂ = 180 g mol-1, ΔT_f2 = ?

= 12.996 K kg mol^-1
≅ 13 K kg mol^-1

∴ Freezing point of solution = T_f
= 273 – 3.801 = 269.2 K
Freezing point of solution = 269.2 K.

Question 11.
A solution of citric acid C₆H₈O₇ in 50 g of acetic acid has a boiling point elevation of 1.76 K. If K_b for acetic acid is 3.07 K kg mol^-1, what is the molality of solution?
Answer:
Given : W₁ = 50 g acetic acid
ΔT_b = 1.76 K
K_b = 3.07 K kg mol^-1
m = ?
ΔT_b = K_b × m
∴ m = \(\frac{\Delta T_{\mathrm{b}}}{K_{\mathrm{b}}}\)
= \(\frac{1.76}{3.07}\)
= 0.5733 m
Molality of solution = 0.5733 m

Question 12.
An aqueous solution of a certain organic compound has a density of 1.063 gmL^-1, an osmotic pressure of 12.16 atm at 25°C and a freezing point of -1.03°C. What is the molar mass of the compound? (334 g/mol)

Question 13.
A mixture of benzene and toluene contains 30% by mass of toluene. At 30°C, vapour pressure of pure toluene is 36.7 mm Hg and that of pure benzene is 118.2 mm Hg. Assuming that the two liquids form ideal solutions, calculate the total pressure and partial pressure of each constituent above the solution at 30°C.
Answer:
Given : 30% by mass of toluene (T) and 70% by mass of benzene (B).
W_T = 30 g; W_B = 70g
\(P_{\mathrm{T}}^{0}\) = 36.7 mm Hg; \(P_{\mathrm{B}}^{0}\) = 118.2 mm Hg
M_T = 92 g mol^-1; MB = 78 g mol^-1
P_T = ?, P_B = ?, P_soln = ?

Total number of moles = n_Total = n_T + n_B
= 0.326 + 0.8974
= 1.2234 mol

Mole fractions :
x_T = \(\frac{n_{\mathrm{T}}}{n_{\text {Total }}}=\frac{0.326}{1.2234}\) = 0.2665
x_B = 1 – 0.2665 = 0.7335
Psoln = x_T + \(P_{\mathrm{T}}^{0}\) + x_B × \(P_{\mathrm{B}}^{0}\)
= 0.2665 × 36.7 + 0.7335 × 118.2
= 9.780 + 86.7
= 96.48 mm Hg

Partial pressures :
P_T = x_T × P_soln
= 0.2665 × 96.48
= 25.71 mm Hg
P_B = x_B × P_soln
= 0.7335 × 96.48
= 70.77 mm Hg
Total pressure P_soln = 96.48 mm Hg
Partial pressures : P_Toluene = 25.71 mm Hg
P_Benzene = 70.77 mm Hg

Question 14.
At 25 °C a 0.1 molal solution of CH₃COOH is 1.35% dissociated in an aqueous solution. Calculate freezing point and osmotic pressure of the solution assuming molality and molarity to be identical.
Answer:
Given : T = 273 + 25 = 298 K
C = 0.1 m ≅ 0.1 M; K_f = 1.86 K kg mol^-1
Per cent dissociation = 1.35
Freezing point = t_f = ?
π = ?
α = \(\frac{1.35}{100}\) = 0.0135

i = 1 – α + α + α = 1 + α = 1 + 0.0135 = 1.0135
(i) ΔT_f = i × K_f × m
= 1.0135 × 1.86 × 0.1
= 0.1885 °C
∴ Freezing point of solution = 0 – 0.1885
= – 0.1885 °C

(ii) n = iCRT
= 1.035 × 0.1 × 0.08206 × 298
= 2.53 atm

(i) Freezing point of solution = – 0.1885 °C
(ii) Osmotic pressure = π = 2.53 atm

Question 15.
A 0.15 m aqueous solution of KCl freezes at -0.510 °C. Calculate i and osmotic pressure at 0 °C. Assume volume of solution equal to that of water.
Answer:
Given : c = 0.15 m KCl ≅ 0.15 M KCl
ΔT_f = 0 – T_f = 0 – (-0.510) = 0.510 °C
T = 273 K; K_f = 1.86 K kg mol^-1
i = ?; π = ?
ΔT_f = i × K_f × m
∴ i = \(\frac{\Delta T_{\mathrm{f}}}{K_{\mathrm{f}} \times m}\)
= \(\frac{0.510}{1.86 \times 0.15}\)
= 1.828
π = iCRT
= 1.828 × 0.15 × 0.08206 × 273
= 6.143 atm
i = 1.828, Osmotic pressure = π = 6.143 atm

12th Chemistry Digest Chapter 2 Solutions Intext Questions and Answers

Can you tell ? (Textbook Page No. 29)

Question 1.
Why naphthalene dissolves in benzene but not in water ?
Answer:
Since naphthalene is a covalent nonpolar substance, it is soluble in a nonpolar solvent like benzene but insoluble in polar solvent like water.

Question 2.
Anhydrous sodium sulphate dissolves in water with the evolution of heat. What is the effect of temperature on its solubility ?
Answer:
Since the dissolution of anhydrous sodium sulphate in water is an exothermic process due to evolution of heat, according to Le Chatelier’s principle its solubility decreases with the increase in temperature.

(Textbook Page No. 42)

Question 1.
If 1.25 m sucrose solution has ΔT_f of 2.32 °C, what will be the expected value of ΔT_f for 1.25 m CaCl₂ solution?
Answer:
Sucrose being nonelectrolyte, it has i = 1 but for CaCl₂,
(CaCl₂ → Ca²⁺ + 2Cl^–) the value of i = 3.
Hence
ΔT_f = i × 2.32
= 3 × 2.32
= 6.92 °C
∴ ΔT_f = 6.92 °C.

(Textbook Page No. 44)

Question 1.
Which of the following solutions will have maximum boiling point elevation and which have minimum freezing point depression assuming the complete dissociation? (a) 0.1m KCl (b) 0.05 m NaCl (c) 1 m AlPO₄ (d) 0.1 m MgSO₄.
Solution :
Boiling point elevation and freezing point depression are colligative properties that depend on number of particles in solution. The solution having more number of particles will have large boiling point elevation and that having less number of particles would show minimum freezing point depression.

AlPO₄ solution contains highest moles and hence highest number particles and in turn, the maximum ΔT_b. NaCl solution has minimum moles and particles, it has minimum ΔT_f.

Question 2.
Arrange the following solutions in order of increasing osmotic pressure. Assume complete ionization. (a) 0.5 m Li₂SO₄ (b) 0.5 m KCl (c) 0.5 m Al₂(SO₄)₃ (d) 0.1 m BaCl₂.
Answer:
Consider 1 dm³ of each solution.

Osmotic pressure being a colligative property, it depends on number of particles in the solution.
Therefore, increasing order of osmotic pressure is,

Maharashtra State Board 12th Std Chemistry Textbook Solutions

• Solid State Class 12 Chemistry Textbook Solutions
• Solutions Class 12 Chemistry Textbook Solutions
• Ionic Equilibria Class 12 Chemistry Textbook Solutions
• Chemical Thermodynamics Class 12 Chemistry Textbook Solutions
• Electrochemistry Class 12 Chemistry Textbook Solutions
• Chemical Kinetics Class 12 Chemistry Textbook Solutions
• Elements of Groups 16, 17 and 18 Class 12 Chemistry Textbook Solutions
• Transition and Inner Transition Elements Class 12 Chemistry Textbook Solutions

Solid State Class 12 Exercise Question Answers Solutions Maharashtra Board

Balbharti Maharashtra State Board 12th Chemistry Textbook Solutions Chapter 1 Solid State Textbook Exercise Questions and Answers.

Class 12 Chemistry Chapter 1 Exercise Solutions Maharashtra Board

Chemistry Class 12 Chapter 1 Exercise Solutions

1. Choose the most correct answer.

Question i.
Molecular solids are
(a) crystalline solids
(b) amorphous solids
(c) ionic solids
(d) metallic solids
Answer:
(b) amorphous solids

Question ii.
Which of the following is n-type semiconductor?
(a) Pure Si
(b) Si doped with As
(c) Si doped with Ga
(d) Ge doped with In
Answer:
(b) Si doped with As

Question iii.
In Frenkel defect
(a) electrical neutrality of the substance is changed.
(b) density of the substance is changed.
(c) both cation and anion are missing
(d) overall electrical neutrality is preserved
Answer:
(d) overall electrical neutrality is preserved

Question iv.
In crystal lattice formed by bcc unit cell the void volume is
(a) 68%
(b) 74%
(c) 32%
(d) 26%
Answer:
(c) 32%

Question v.
The coordination number of atoms in bcc crystal lattice is
(a) 2
(b) 4
(c) 6
(d) 8
Answer:
(d) 8

Question vi.
Which of the following is not correct ?
(a) Four spheres are involved in the formation of tetrahedral void.
(b) The centres of spheres in octahedral voids are at the a pices of a regular tetrahedron.
(c) If the number of atoms is N the number of octahedral voids is 2N.
(d) If the number of atoms is N/2, the number of tetrahedral voids is N.
Answer:
(c) If the number of atoms is N the number of octahedral voids is 2N.

Question vii.
A compound forms hcp structure. Number of octahedral and tetrahedral voids in 0.5 mole of substance is respectively
(a) 3.011 × 10²³, 6.022 × 10²³
(b) 6.022 × 10²³, 3.011 × 10²³
(c) 4.011 × 10²³, 2.011 × 10²³
(d) 6.011 × 10²³, 12.022 × 10²³
Answer:
(a) 3.011 × 10²³, 6.022 × 10²³

Question viii.
Pb has fcc structure with edge length of unit cell 495 pm. Radius of Pb atom is
(a) 205 pm
(b) 185 pm
(c) 260 pm
(d) 175 pm
Answer:
(d) 175 pm

2. Answer the following in one or two sentences.

Question i.
What are the types of particles in each of the four main classes of crystalline solids?
Answer:
The smallest constituents or particles of various solids are atoms, ions or molecules.

Question ii.
Which of the three types of packing used by metals makes the most efficient use of space and which makes the least efficient use ?
Answer:
fcc has the most efficient packing of particles while scc has the least efficient packing.

Question iii.
The following pictures show population of bands for materials having different electrical properties. Classify them as insulator, semiconductor or a metal.

Answer:
Picture A represents metal conductor,
Picture B represents insulator,
Picture C represents semiconductor.

Question iv.
What is a unit cell?
Answer:

• Unit cell : It is the smallest repeating structural unit of a crystalline solid (or crystal lattice) which when repeated in different directions produces the crystalline solid (lattice).
• The crystal is considered to consist of an infinite number of unit cells.
• The unit cell possesses all the characteristics of the crystalline solid.

Question v.
How does electrical conductivity of a semiconductor change with temperature ? Why?
Answer:

• Since the energy difference between valence band and conduction band in semiconductor is not large, the electrons from valence band can be promoted to conduction by heating.
• Hence electrical conductivity of a semiconductor increases with temperature.

Question vi.
The picture represents bands of MOs for Si. Label valence band, conduction band and band gap.

Answer:

Question vii.
A solid is hard, brittle and electrically non-conductor. Its melt conducts electricity. What type of solid is it?
Answer:
A solid crystalline electrolyte like NaCl is hard, brittle and electrically nonconductor. But its melt conducts electricity.

Question viii.
Mention two properties that are common to both hep and ccp lattices.
Answer:
In hcp and ccp crystal lattices coordination number is 12 and packing efficiency is 74%.

Question ix.
Sketch a tetrahedral void.
Answer:

Question x.
What are ferromagnetic substances?
Answer:

1. The substances which possess unpaired electrons and high paramagnetic character and when placed in a magnetic field are strongly attracted and show permanent magnetic moment even when the external magnetic field is removed are said to be ferromagnetic. They can be permanently magnetised.
2. In the solid state, the metal ions of ferromagnetic substance are grouped together into small regions called domains, where each domain acts as a tiny magnet.

For example : Fe, Co, Gd, Ni, CrO₂, etc.

3. Answer the following in brief.

Question i.
What are valence band and conduction band?
Answer:
There are two types of bands of molecular orbitals as follows :

• Valence band : The atomic orbitals with filled electrons from the inner shells form valence bands, where there are no free mobile electrons since they are involved in bonding.
• Conduction band : Atomic orbitals which are partially filled or empty on overlapping form closely placed molecular orbitals giving conduction bands where electrons are delocalised and can conduct, heat and electricity.

Question ii.
Distinguish between ionic solids and molecular solids.
Answer:

Question iii.
Calculate the number of atoms in fcc unit cell.
Answer:
Number of atoms in face-centred cubic (fcc) unit cell :
In this unit cell, there are 8 atoms at 8 corners and 6 atoms at 6 face centres. Each corner contributes 1/8th atom to the unit cell, hence due to 8 corners,
Number of atoms = \(\frac {1}{8}\) × 8 = 1.
Each face centre contributes half of the atom to the unit cell, hence due to 6 face centres,
Number of atoms = \(\frac {1}{2}\) × 6 = 3.
∴ Total number of atoms present in fee unit cell = 1 + 3 = 4.
Hence the volume of the unit cell is equal to the volume of four atoms.

Face centered unit cell

Question iv.
How are the spheres arranged in first layer of simple cubic close-packed structures? How are the successive layers of spheres placed above this layer ?
Answer:
(i) Stacking of square close packed layers :

Stacking of square close packed layers

In this arrangement, the two dimensional AAAA type square closed packed layers are placed one over the other in such a way that the crests of all spheres are in contact with successive layers in all directions. All spheres of different layers are perfectly aligned horizontally and vertically forming unit cells having primitive or simple cubic structure. Since all the layers are identical and if each layer is labelled as layer A, then whole three dimensional crystal lattice will be of AAAA… type.

Each sphere is in contact with six surrounded spheres, hence the coordination number of each sphere is six.

(ii) Stacking of two hexagonal close packed layers :
A close packed three dimensional structure can be generated by arranging hexagonal close packed layers in a particular manner.

In this the spheres of second layer are placed in the depression of the first layer.
In this if first layer is labelled as A then second layer is labelled as B since they are aligned differently.

Two layers of closed packed spheres

In this, all triangular voids of the first layers are not covered by the spheres of the second layer. The triangular voids which are covered by second layer spheres generate tetrahedral void which is surrounded by four spheres. The triangular voids in one layer have above them triangular voids of successive layers.

The overlapping triangular voids from two layers together form an octahedral void which is surrounded by six spheres.

Question v.
Calculate the packing efficiency of metal crystal that has simple cubic structure.
Answer:
Step 1 : Radius of sphere : In simple cubic lattice, the atoms (spheres) are present at eight corners and in contact along the edge in the unit cell.
If ‘a’ is the edge length of the unit cell and ‘r’ is the radius of the atom, then
a = 2r or r = a/2

scc structure

Step 2 : Volume of sphere :
Volume of one particle = \(\frac{4 \pi}{3}\) × r³
= \(\frac{4 \pi}{3}\) × (a/2)³ = \(\frac{\pi a^{3}}{6}\)

Step 3 : Total volume of particles : Since the unit cell contains one particle. Volume occupied by one particle in unit cell = \(\frac{\pi a^{3}}{6}\)

Step 4 : Packing efficiency :
Packing efficiency

∴ Packing efficiency = 52.36%
Percentage of void space = 100 – 52.36
= 47.64%

Question vi.
What are paramagnetic substances? Give examples.
Answer:
(1) The magnetic properties of a substance arise due to the presence of electrons.
(2) An electron while revolving around the nucleus, also spins around its own axis and generates a magnetic moment and magnetic properties.
(3) If an atom or a molecule contains one or more unpaired electrons spinning in same direction, clockwise or anticlockwise, then the substance is associated with net magnetic moment and magnetic properties. They experience a net force of attraction when placed in the magnetic field. This phenomenon is called paramagnetism and the substance is said to be paramagnetic.
For example, O₂, Cu²⁺, Fe³⁺ , Cr³⁺ , NO, etc.

Question vii.
What are the consequences of Schottky defect?
Answer:
Consequences of Schottky defect :

• Since the number of ions (cations and anions) decreases but volume remains unchanged, the density of a substance decreases.
• As the number of missing cations and anions is equal, the electrical neutrality of the compound remains same.
• This defect arises in ionic crystals like NaCl, AgBr, KCl, etc.

Question viii.
Cesium chloride crystallizes in cubic unit cell with Cl^– ions at the corners and Cs⁺ ion in the centre of the cube. How many CsCl molecules are there in the unit cell ?
Answer:
Number of Cs⁺ ion at body centre = 1
Number of Cl^– ions due to 8 comers = 8 × \(\frac {1}{8}\) = 1
Hence unit cell contains 1 CsCl molecule.

Question ix.
Cu crystallizes in fee unit cell with edge length of 495 pm. What is the radius of Cu atom ?
Answer:
Given : a = 495 pm
Radius, r = ?
For fee structure,
radius = r = \(\frac{a}{2 \sqrt{2}}=\frac{495}{2 \times \sqrt{2}}\) = 175 cm.
Radius of Cu atom = 175 pm

Question x.
Obtain the relationship between density of a substance and the edge length of unit cell.
Answer:
(1) Consider a cubic unit cell of edge length ‘a’.
The volume of unit cell = a³

(2) If there are ‘n’ particles per unit cell and the mass of particle is ‘m’, then
Mass of unit cell = m × n.

(3) If the density of the unit cell of the substance is p then
Density of unit cell = \(\frac{\text { Mass of unit cell }}{\text { Volume of unit cell }}\)
ρ = \(\frac{m \times n}{a^{3}}\)

Question 4.
The density of iridium is 22.4 g/cm³. The unit cell of iridium is fcc. Calculate the radius of iridium atom. Molar mass of iridium is 192.2 g/mol.
Answer:
Given : Crystal structure of iridium = fcc
Molar mass of iridium = 192.2 gmol^-1
Density = ρ = 22.4 gcm^-3
Radius of iridium = ?
In fcc structure, there are 8 Ir atoms at 8 comers and 6 Ir atoms at 6 face centres.
∴ Total number of Ir atoms = \(\frac {1}{8}\) × 8 + \(\frac {1}{2}\) × 6
= 1 + 3
= 4
Mass of Ir atom = \(\frac{192.2}{6.022 \times 10^{23}}\)
= 31.92 × 10^-23 g
∴ Mass of 4 Ir atoms = 4 × 31.92 × 10^-23
= 1.277 × 10^-21 g
∴ Mass of unit cell = 1.277 × 10^-21 g
Density of unit cell = \(\frac{\text { Mass of unit cell }}{\text { Volume of unit cell }}\)
22.4 = \(\frac{1.277 \times 10^{-21}}{a^{3}}\)
∴ a³ = \(\frac{1.277 \times 10^{-21}}{22.4}\)
= 57 × 10^-24 cm³
∴ a = (57 × 10^-24)³ = 3.848 × 10^-8 cm
If r is the radius of iridium atom, then for fcc structure,
r = \(\frac{a}{2 \sqrt{2}}\)
= \(\frac{3.848 \times 10^{-8}}{2 \times 1.414}\)
= 1.36 × 10^-8 cm
= 136 pm
Radius of iridium atom = 136 pm

Question 5.
Aluminium crystallizes in cubic close packed structure with unit cell edge length of 353.6 pm. What is the radius of Al atom ? How many unit cells are there in 1.00 cm³ of Al ?
Answer:
Given : Structure of Al
= Cubic close packed structure
= ccp structure
Edge length of unit cell = a = 353.6 pm
= 3.536 × 10^-8 cm
r = ?
Number of unit cells in 1.00 cm³ of Al = ?
Radius of Al atom = r = \(\frac{a}{2 \sqrt{2}}=\frac{353.6}{2 \sqrt{2}}\)
= \(\frac{353.6}{2 \times 1.414}\) = 125 pm
Volume of one unit cell = a³ = (3.536 × 10^-8)³
= 4.421 × 10^-23 cm³
Number of unit cells = \(\frac{1.00}{4.421 \times 10^{-23}}\)
= 2.26 × 10²²
Radius of Al atom = 125 pm
Number of unit cells = 2.26 × 10²²

Question 6.
In an ionic crystalline solid atoms of element Y form hcp lattice. The atoms of element X occupy one third of tetrahedral voids. What is the formula of the compound?
Answer:
In the given hcp lattice, Y atoms are present at 12 corners and 2 face centres.
∴ Number of Y atoms = \(\frac {1}{2}\) × 12 + 2 × \(\frac {1}{2}\) = 3
There are 6 tetrahedral voids, the number of X atoms = \(\frac {1}{3}\) × 6 = 2
∴ Formula of the compound is X₂Y₃.

Question 7.
How are tetrahedral and octahedral voids formed?
Answer:
Tetrahedral void : The vacant space or void among four constituent particles having tetrahedral arrangement in the crystal lattice is called tetrahedral void.

The arrangement of four spheres around the void is tetrahedral. A tetrahedral void is formed when a triangular void made by three coplanar spheres is in contact with fourth sphere above or below it.

Octahedral void : The vacant space or void at the centre of six spheres (or atoms) which are placed octahedrally is called octahedral void.

Question 8.
Third layer of spheres is added to second layer so as to form hcp or ccp structure. What is the difference between the addition of third layer to form these hexagonal close-packed structures?
Answer:

1. In the formation of hexagonal closed-packed (hcp) structure, the first one dimensional row shows depressions between neighbouring atoms.
2. When a second row is arranged so that spheres fit in these depressions then a staggered arrangement is obtained. If the first row is A then the second row is B.
3. When third row is placed in staggered manner in contact with second row then A type arrangement is obtained.
4. Similarly, the spheres in fourth row can be arranged as B type layer. This results in ABAB… type setting of the layers. This gives hexagonal close packing (hcp) structure.

Hexagonal close packing (hcp)

Question 9.
An element with molar mass 27 g/mol forms cubic unit cell with edge length of 405 pm. If density of the element is 2.7 g/cm³, what is the nature of cubic unit cell ? (fcc or ccp)
Answer:
Given : Molar mass = M = 27 g mol^-1
Nature of crystal = cubic unit cell
Edge length = a = 405 pm = 4.05 × 10^-8 cm
Density = ρ = 2.7 g cm^-3
Nature of unit cell = ?

= 3.997
≅ 4
Hence the nature of unit cell = face-centred cubic unit cell
Radius of Al atom = 125 pm
The nature of cubic unit cell is fcc.

Question 10.
An element has a bcc structure with unit cell edge length of 288 pm. How many unit cells and number of atoms are present in 200 g of the element? (1.16 × 10²⁴, 2.32 × 10²⁴)

Question 11.
Distinguish with the help of diagrams metal conductors, insulators and semiconductors from each other.
Answer:
Conductor:

1. A substance which conducts heat and electricity to a greater extent is called conductor.
2. In this, conduction bands and valence bands overlap or are very closely spaced.
3. There is no energy difference or very less energy difference between valence bands and conduction bands.
4. There are free electrons in the conduction bands.
5. The conductance decreases with the increase in temperature.
6. E.g., Metals, alloys.
7. The conducting properties can’t be improved by adding third substance.

Insulator:

1. A substance which cannot conduct heat and electricity under any conditions is called insulator.
2. In this, conduction bands and valence bands are far apart.
3. The energy difference between conduction bands and valence bands is very large.
4. There are no free electrons in the conduction bands and electrons can’t be excited from valence bands to conduction bands due to large energy difference.
5. No effect of temperature on conducting properties.
6. E.g., Wood, rubber, plastics.
7. No effect of addition of any substance.

Semiconductor:

1. A substance that has poor electrical conductance at low temperature but higher conductance at higher temperature is called semiconductor.
2. In this, conduction bands and valence bands are spaced closely.
3. The energy difference between conduction bands and valence bands is small.
4. The electrons can be easily excited from valence bands to conduction bands by heating.
5. Conductance increases with the increase in temperature.
6. E.g., Si, Ge
7. By doping, conducting properties improve. E.g. n-type, p-type semiconductors.

Question 12.
What are n-type semiconductors? Why is the conductivity of doped n-type semiconductor higher than that of pure semiconductor ? Explain with diagram.
Answer:
n-type semiconductor:

• n-type semiconductor contains increased number of electrons in the conduction band.
• When Si semiconductor is doped with 15^th group element phosphorus, P, the new atoms occupy some vacant sites in the lattice in place of Si atoms.
• P has five valence electrons, out of which four are involved in covalent bonding with neighboring Si atoms while one electrons remains free and delocalised.
• These free electrons increase the electrical conductivity of the semiconductor.
• The semiconductors with extra non-bonding free electrons are called n-type semiconductors.

P atom occupying regular site of Si atom

Question 13.
Explain with diagram. Frenkel defect. What are the conditions for its formation? What is its effect on density and electrical neutrality of the crystal?
Answer:

1. Frenkel defect : This defect arises when an ion of an ionic compound is missing from its regular site and occupies interstitial vacant position between lattice points.
2. Cations have smaller size than anions, hence generally cations occupy the interstitial sites.
3. This creates a vacancy defect at its original position and interstitial defect at new position.
4. Frenkel defect is regarded as the combination of interstitial defect and vacancy defect.

Conditions for the formation of Frenkel defect :

1. This defect arises in ionic compounds with a large difference between the sizes of cation and anion.
2. The ionic compounds must have ions with low coordination number.

Consequences of Frenkel defect :

1. Since there is no loss of ions from the crystal lattice, the density of the solid remains unchanged.
2. The crystal remains electrically neutral.
3. This defect is observed in ZnS, AgCl, AgBr, Agl, CaF₂, etc.

Question 14.
What is an impurity defect? What are its types? Explain the formation of vacancies through aliovalent impurity with example.
Answer:
Impurity defect : This defect arises when foreign atoms, that is, atoms different from the host atoms are present in the crystal lattice.

There are two types of impurity defects namely

1. Substitutional defects and
2. Interstitial defects.

(1) Substitutional defects : These defects arises when foreign atoms occupy the lattice sites in place of host atoms, due to their displacements.
Examples : Solid solutions of metals (alloys). For example. Brass in which host atoms are of Cu which are replaced by impurity of Zn atoms. In this Zn atoms occupy regular sites while Cu atoms occupy substituted sites.

Brass

Vacancy through aliovalent impurity :
By addition of impurities of aliovalent ions :

Vacancy through aliovalent ion

When aliovalent ion like Sr²⁺ in small amount is added by additing SrCl₂ to NaCl during its crystallisation, each Sr²⁺ ion (oxidation state 2+) removes 2 Na⁺ ions from their lattice points, to maintain electrical neutrality. Hence one of vacant lattice site is occupied by Sr²⁺ ion while other site remains vacant.

Interstitial impurity defect :

Stainless steel

A defect in solid in which the impurity atoms occupy interstitial vacant spaces of lattice structure is called interstitial impurity defect.

For example, in steel, normal lattice sites are occupied by Fe atoms but interstitial spaces are occupied by carbon atoms.

12th Chemistry Digest Chapter 1 Solid State Intext Questions and Answers

Try this… (Textbook Page No. 1)

Observe the above figure carefully. The two types of circles in this figure represent two types of constituent particles of a solid.

Question 1.
Will you call the arrangement of particles in this solid regular or irregular ?
Answer:
The arrangement of particles in this solid is regular.

Question 2.
Is the arrangement of constituent particles in directions \(\overrightarrow{\mathbf{A B}}\), \(\overrightarrow{\mathbf{C D}}\) and \(\overrightarrow{\mathbf{E F}}\) same or different?
Answer:
\(\overrightarrow{\mathbf{A B}}\) represents arrangement of identical particles of one type.
\(\overrightarrow{\mathbf{C D}}\) represents arrangement of identical particles of another type.
\(\overrightarrow{\mathbf{E F}}\) represents regular arrangement of two different particles in alternate positions.

Use your brain power ! (Textbook Page No. 2)

Question 1.
Identify the arrangements A and B as crystalline or amorphous.

Answer:
Arrangement in image A indicates the substance is crystalline.
Arrangement in image B indicates the substance is amorphous.

Try this… (Textbook Page No. 3)

Question 1.
Graphite is a covalent solid yet soft and good conductor of electricity. Explain.
Answer:

1. Each carbon atom in graphite is sp² hybridised and covalently bonded to other three sp2 hybridised carbon atoms forming σ bonds and the fourth electron in 2p_z orbital of each carbon atom is used in the formation of a π bond. This results in the formation of hexagonal rings in two dimensions.
2. In graphite, the layers consisting of hexagonal carbon network are held together by weak van der Waal’s forces imparting softness.
3. The electrons in π bonds in the ring are delocalised and free to move in the delocalised molecular orbitals giving good electrical conductance.

Use your brain power ! (Textbook Page No. 13)

Question 1.
Which of the three lattices scc, bcc and fcc has the most efficient packing of particles ? Which one has the least efficient packing ?
Answer:
fcc has the most efficient packing of particles while see has the least efficient packing.

Can you think ? (Textbook Page No. 20)

Question 1.
When ZnO is heated it turns yellow and returns back to original white colour on cooling. What could be the reason ?
Answer:
When colourless ZnO is strongly heated, the metal atoms are deposited on crystal surface and anions O^2- migrate to the surface producing vacancies at anion lattice points.

These anions combine with Zn atoms forming ZnO and release electrons.
Zn + O^2- → ZnO + 2e^–

These released electrons diffuse into the crystal and occupy vacant sites of anions and produce F- centres. Due to these colour centres, ZnO turns yellow.

Can you tell ? (Textbook Page No. 23)

Let a small quantity of phosphorus be doped into pure silicon.

Question 1.
Will the resulting material contain the same number of total number of electrons as the original pure silicon ?
Answer:
Total number of electrons in doped silicon will be more than in original silicon.

Question 2.
Will the material be electrically neutral or charged ?
Answer:
Material will be electrically neutral.

Maharashtra State Board 12th Std Chemistry Textbook Solutions

• Solid State Class 12 Chemistry Textbook Solutions
• Solutions Class 12 Chemistry Textbook Solutions
• Ionic Equilibria Class 12 Chemistry Textbook Solutions
• Chemical Thermodynamics Class 12 Chemistry Textbook Solutions
• Electrochemistry Class 12 Chemistry Textbook Solutions
• Chemical Kinetics Class 12 Chemistry Textbook Solutions
• Elements of Groups 16, 17 and 18 Class 12 Chemistry Textbook Solutions
• Transition and Inner Transition Elements Class 12 Chemistry Textbook Solutions

Semiconductor Devices Class 12 Exercise Question Answers Solutions Maharashtra Board

Balbharti Maharashtra State Board 12th Physics Textbook Solutions Chapter 16 Semiconductor Devices Textbook Exercise Questions and Answers.

Class 12 Physics Chapter 16 Exercise Solutions Maharashtra Board

Physics Class 12 Chapter 16 Exercise Solutions

1. Choose the correct option

i.
In a BJT, the largest current flow occurs
(A) in the emitter
(B) in the collector
(C) in the base
(D) through CB junction.
Answer:
(A) in the emitter

ii.
A series resistance is connected in the Zener diode circuit to
(A) properly reverse bias the Zener
(B) protect the Zener
(C) properly forward bias the Zener
(D) protect the load resistance.
Answer:
(A) properly reverse bias the Zener

iii.
An LED emits visible light when its
(A) junction is reverse biased
(B) depletion region widens
(C) holes and electrons recombine
(D) junction becomes hot.
Answer:
(C) holes and electrons recombine

iv.
Solar cell operates on the principle of
(A) diffusion
(B) recombination
(C) photovoltaic action
(D) carrier flow.
Answer:
(C) photovoltaic action

v.
A logic gate is an electronic circuit which
(A) makes logical decisions
(B) allows electron flow only in one direction
(C) works using binary algebra
(D) alternates between 0 and 1 value.
Answer:
(A) makes logical decisions

2 Answer in brief.

i.
Why is the base of a transistor made thin and is lightly doped?
Answer:
The base of a transistor is lightly doped than the emitter and is made narrow so that virtually all the electrons injected from the emitter (in an npn tran-sistor) diffuse right across the base to the collector junction without recombining with holes. That is, the base width is kept less than the recombination distance. Also, the emitter is much heavily doped than the base to improve emitter efficiency and common-base current gain a.

ii.
How is a Zener diode different than an ordinary diode?
Answer:
A Zener diode is heavily doped-the doping con-centrations for both p- and n-regions is greater than 1018 cm-3 while those of an ordinary diode are voltage (PIV) of an ordinary diode is higher than a Zener diode and the breakdown occurs by impact ionization (avalanche process). Their I-V characteristics are otherwise similar.

iii.
On which factors does the wavelength of light emitted by a LED depend?
Answer:
The intensity of the emitted light is directly propor-tional to the recombination rate and hence to the diode forward current. The colour of the light emitted by an LED depends on the compound semiconductor material used and its composition (and doping levels) as given below :
Table: Typical semiconductor materials and emitted colours of LEDs

iv.
Why should a photodiode be operated in reverse biased mode?
Answer:
A photodiode is operated in a reverse biased mode because as photodetector or photosensor, it must conduct only when radiation is incident on it. In the reverse biased mode, the dark current for zero illumination is negligibly small—of the order of few picoamperes to nanoamperes. But when illuminated, the photocurrent is several orders of magnitude greater.

v.
State the principle and uses of a solar Cell.
Answer:
A solar cell is an unbiased pn-junction that converts the energy of sunlight directly into electricity with a high conversion efficiency.

Principle : A solar cell works on the photovoltaic effect in which an emf is produced between the two layers of a pn-junction as a result of irradiation.

Question 3.
Draw the circuit diagram of a half wave rectifier. Explain its working. What is the frequency of ripple in its output?
Answer:
A device or a circuit which rectifies only one-half of each. cycle of an alternating voltage is called a half-wave rectifier.
Electric circuit : The alternating voltage to be rectified is applied across the primary coil (P₁P₂) of a transformer. The secondary coil (S₁S₂) of the transformer is connected in series with the junction diode and a load resistance R_L, as shown in below figure. The alternating voltage across the secondary coil is the ac input voltage V_i. The dc voltage across the load resistance is called the output voltage V₀.

Working : Due to the alternating voltage V_i, the p-region of the diode becomes alternatively positive and negative with respect to the n-region.
During the half-cycle when the p-region is positive, the diode is forward biased and conducts. A current I_L passes through the load resistance RL in the direction shown.

During the next half cycle, when the p-region is negative, the diode is reverse biased and the forward current drops to zero.

Thus, the diode conducts only during one-half of the input cycle and thus acts as a half-wave rectifier. The intermittent output voltage V₀ has a fixed polarity but changes periodically with time between zero and a maximum value. I_L is unidirectional. Above figure shows the input and output voltage waveforms.

The pulsating dc output voltage of a half-wave rectifier has the same frequency as the input.

Question 4.
Why do we need filters in a power supply?
Answer:
A rectifier-half-wave or full-wave – outputs a pul-sating dc which is not directly usable in most electronic circuits. These circuits require something closer to pure dc as produced by batteries. Unlike pure dc waveform of a battery, a rectifier output has an ac ripple riding on a dc waveform.

The circuit used in a dc power supply to remove the ripple is called a filter. A filter circuit can produce a very smooth waveform that approximates the waveform produced by a battery. The most common technique used for filtering is a capacitor connected across the output of a rectifier.

Question 5.
Draw a neat diagram of a full wave rectifier and explain it’s working.
Answer:
A device or a circuit which rectifies both halves of each cycle of an alternating voltage is called a full-wave rectifier.
Electric circuit : The alternating voltage to be rectified is applied across the primary coil (P₁P₂) of a transformer with a centre-tapped secondary coil (S₁S₂). The terminals and S2 of the secondary are connected to the two p-regions of two junction diodes D₁ and D₂, respectively. The centre-tap T is connected to the ground. The load resistance RL is connected across the common n-regions and the

P₁P₂, S₁S₂ : Primary and secondary of transformer,
T : Centre-tap on secondary; D₁ D₂ : Junction diodes,
R_L : Load resistance, I_L : Load current,
V_i: AC input voltage, V₀ : DC output voltage
Above Figure : Full-wave rectifier circuit

Working : During one half cycle of the input, terminal S₁ of the secondary is positive while S₂ is negative with respect to the ground (the centre-tap T). During this half cycle, diode D₁ is forward biased and conducts, while diode D₂ is reverse biased and does not conduct. The direction of current Z_L through R_L is in the sense shown.

During the next half cycle of the input voltage, S2 becomes positive while S, is negative with respect to T. Diode D2 now conducts sending a current IL through RL in the same sense as before. Dt now does not conduct. Thus, the current through RL flows in the same direction, i.e., it is unidirectional, for both halves or the full-wave of the input. This is called full-wave rectification.

The output voltage has a fixed polarity but varies periodically with time between zero and a maximum value. Above figure shows the input and output voltage waveforms. The pulsating dc output voltage of a full-wave rectifier has twice frequency of the input.

Question 6.
Explain how a Zener diode maintains constant voltage across a load.
Answer:
Principle : In the breakdown region of a Zener diode, for widely changing Zener current, the voltage across the Zener diode remains almost constant.

Electric circuit : The circuit for regulating or stabilizing the voltage across a load resistance RL against change in load current and supply voltage is shown in above figure. The Zener diode is connected parallel to load Rh such that the current through the Zener diode is from the n to p region. The series resistance Rs limits the current through the diode below the maximum rated value.
From the circuit, I = I_Z + I_L and V = IR_s + V_Z
= (I_Z + I_L)R_s + V_Z
Working: When the input unregulated dc voltage V across the Zener diode is greater than the Zener voltage V_Z in magnitude, the diode works in the Zener breakdown region. The voltage across the diode and load Rh is then V_Z. The corresponding current in the diode is I_Z.

As the load current (I) or supply voltage (V) changes, the diode current (7Z) adjusts itself at constant V_Z. The excess voltage V-V_Zappears across the series resistance Rs.

For constant supply voltage, the supply current I and the voltage drop across R_s remain constant. If the diode is within its regulating range, an increase in load current is accompanied by a decrease in Iz at constant V_Z.
Since the voltage across R_L remains constant at V_Z, the Zener diode acts as a voltage stabilizer or voltage regulator.

Question 7.
Explain the forward and the reverse characteristic of a Zener diode.
Answer:
The forward bias region of a Zener diode is identical to that of a regular diode. There is forward current only after the barrier potential of the pn- junction is overcome. Beyond this threshold or cut in voltage, there is an exponential upward swing.

The typical forward voltage at room temperature with a current of around 1 mA is around 0.6 V.

In the reverse bias condition the Zener diode is an open circuit and only a small reverse saturation current flows as shown with change of scale. At the reverse breakdown voltage there is an abrupt rapid increase in the current-the knee is very sharp, followed by an almost vertical increase in current. The voltage across the Zener diode in the breakdown region is very nearly constant with only a small increase in voltage with increasing current. There is a minimum Zener current, I_Z (min), that places the operating point in the desired breakdown region. At some high current level, I_ZM, the power dissipation of the diode becomes excessive beyond which the diode can be damaged.

Zener diode characteristics

The I-V characteristics of a Zener diode is not totally vertical in the breakdown region. This means that for slight changes in current, there will be a small change in the voltage across the diode. The voltage change for a given change in current is the resistance R_Z of the Zener diode.

Question 8.
Explain the working of a LED.
Answer:
Working :
An LED is forward-biased with about 1.2 V to 3.6 V at 12 mA to 20 mA. Majority carriers electrons from n-type layer and holes from p-type layer are injected into the active layer. Electrons cross the junction into the p-layer. In the active p-layer, some of these excess minority carriers electrons, recombine radiatively with majority carriers, holes, thereby emitting photons. The resulting photon has an energy approximately equal to the bandgap of the active layer material. Modifying the bandgap of the active layer creates photons of diferent energies.

In the energy band diagram this recombination is equivalent to a transition of the electron from a higher energy state in the conduction band to a lower energy state in the valence band. The energy difference is emitted as a photon of energy hv.
[Note : The photons originate primarily in the p-side of the junction which has a bandgap E_Gp narrower than that of the n-side, E_Gn. Thus, with hv < E_Gn, the photons are emitted through the wide-bandgap n-region with essentially no absorption.]

Question 9.
Explain the construction and working of solar cell.
Answer:
Construction :
A simple pn-junction solar cell con-sists of a p-type semiconductor substrate backed with a metal electrode back contact. A thin n-layer (less than 2.5 pm, for silicon) is grown over the p-type substrate by doping with suitable donor impurity. Metal finger electrodes are prepared on top of the n-layer so that there is enough space between the fingers for sunlight to reach the n-layer and, subsequently, the underlying pn-junction.

Working : When exposed to sunlight, the absorption of incident radiation (in the range near-UV to infrared) creates electron-hole pairs in and near the depletion layer.

Consider light of frequency v incident on the pn-junction such that the incident photon energy hv is greater than the band gap energy EG of the semiconductor. The photons excite electrons from the valence band to the conduction band, leaving vacancies or holes in the valence band, thus generating electron-hole pairs.

The photogenerated electrons and holes move towards the n side and p side, respectively. If no external load is connected, these photogenerated charges get collected at the two sides of the junction and give rise to a forward photovoltage. In a closed- circuit, a current I passes through the external load as long as the solar cell is exposed to sunlight.

A solar cell module consists of several solar cells connected in series for a higher voltage output. For outdoor use with higher power output, these modules are connected in different series and parallel combinations to form a solar cell array.

[Note : Currently most of the crystalline solar cells are p-type as described above. This is because of a lower cost of production of p-type. But performance wise, n-type solar cells (a thin p-layer over an n-type substrate by doping with suitable acceptor impurity) can give much better efficiency compared to p-type solar cells.]

Question 10.
Explain the principle of operation of a photodiode.
Answer:
Construction:
A photodiode consists of an n-type silicon substrate with a metal electrode back contact. A thin p-type layer is grown over the n-type substrate by diffusing a suitable acceptor dopant.

The area of the p-layer defines the photodiode active area. An ohmic contact pad is deposited on the active area. The rest of the active area is left open with a protective antireflective coating of silicon nitride to minimize the loss of photons. The nonactive area is covered with an insulating opaque SiO₂ coating.

Depending on the required spectral sensitivity, i.e., the operating wavelength range, typical photodiode materials are silicon, germanium, indium gallium arsenide phosphide (InGaAsP) and indium gallium arsenide (InGaAs), of which silicon is the cheapest while the last two are expensive.

Working : The band gap energy of silicon is E_G = 1.12 eV at room temperature. Thus, photons or particles with energies greater than or equal to 1.12 eV, which corresponds to 110 nm, can transfer electrons from the valence band into the conduction band.

A photodiode is operated in the reverse bias mode which results in a wider depletion region. When operated in the dark (zero illumination), there is a reverse saturation current due solely to the thermally generated minority charge carriers. This is called the dark current. Depending on the minority carrier concentrations, the dark current in an Si photodiode may range from 5 pA to 10 nA.

When exposed to radiation of energy hv ≥ E_G (in the range near-UV to near-IR), electron-hole pairs are created in the depletion region. The electric field in the depletion layer accelerates these photogenerated electrons and holes towards the n side and p side, respectively, constituting a photocurrent l in the external circuit from the p side to the n side. Due to the photogeneration, more charge carriers are available for conduction and the reverse current is increased. The photocurrent is directly propor-tional to the intensity of the incident light. It is independent of the reverse bias voltage.
[Notes : Typical photodiode materials are :
(1) silicon (Si) : low dark current, high speed, good sensitivity between ~ 400 nm and 1000 run (best around 800 nm-900 nm)
(2) germanium (Ge) : high dark current, slow speed, good sensitivity between ~ 900 nm and 1600 nm (best around 1400 nm-1500 nm)
(3) indium gallium arsenide phosphide (InGaAsP) : expensive, low dark current, high speed, good sensitivity between ~ 1000 nm and 1350 nm (best around 1100 nm- 1300 nm)
(4) indium gallium arsenide (InGaAs): expensive, low dark current, high speed, good sensitivity between ~ 900 nm and 1700 nm (best around 1300 nm-1600 nm],

Question 11.
What do you mean by a logic gate, a truth table and a Boolean expression?
Answer:
A logic gate is a basic switching circuit used in digital circuits that determines when an input pulse can pass through to the output. It generates a single output from one or more inputs.

Explanation/Uses :
Any digital computation process consists in performing a sequence of arithmetical operations on the data of the problem. At each stage in the computation, the nature of the operation to be performed is decided partly by the pre-determined program and partly by the outcome of earlier stages in the process. We therefore need switches with multiple inputs to perform logical operations, i.e., the outputs of these switches are determined in specified ways by the condition (binary state) of their inputs. These arrangements are known as logic gates, and mostly they are extension of a simple transistor switch.

(1) Boolean expression : An equation expressing a logical compound statement in Boolean algebra is called a Boolean expression. A Boolean expression for a logic gate expresses the relation between input(s) and output of a logic gate.

(2) Truth table : The table which shows the truth values of a Boolean expression for a logic gate for all possible combinations of its inputs is called the truth table of logic gate.

The truth table contains one row for each input combination. Since a logical variable can assume only two possible values, 0 and 1, there are 2N combinations of N inputs so that the table has 2N rows.
[Note : Boolean algebra is a form of symbolic logic developed in 1847 by George Boole (1815-64) British mathematician.]

Question 12.
What is logic gate? Write down the truth table and Boolean expression for ‘AND’ gate.
Answer:
A logic gate is a basic switching circuit used in digital circuits that determines when an input pulse can pass through to the output. It generates a single output from one or more inputs.

The AND gate : It is a circuit with two or more inputs and one output in which the output signal is HIGH if and only if all the inputs are HIGH simultaneously.

The AND operation represents a logical multiplication.

Below figure shows the 2-input AND gate logic symbol and the Boolean expression and the truth table for the AND function.
Logic symbol:

Truth table:

Boolean expression:
Y = A ∙ B

Question 13.
What are the uses of logic gates? Why is a NOT gate known as an inverter?
Answer:
Explanation/Uses :
Any digital computation process consists in performing a sequence of arithmetical operations on the data of the problem. At each stage in the computation, the nature of the operation to be performed is decided partly by the pre-determined program and partly by the outcome of earlier stages in the process. We therefore need switches with multiple inputs to perform logical operations, i.e., the outputs of these switches are determined in specified ways by the condition (binary state) of their inputs. These arrangements are known as logic gates, and mostly they are extension of a simple transistor switch.

The NOT gate or INVERTER : It is a circuit with one input whose output is HIGH if the input is LOW and vice versa.

The NOT operation outputs an inverted version of the input. Hence, a NOT gate is also known as an INVERTER.

The small invert bubble on the output side of the inverter logic symbol, below figure and the over bar (^–) in the Boolean expression represent the invert function.

Question 14.
Write the Boolean expression for (i) OR gate, (ii) AND gate, and (iii) NAND Gate.
Answer:
(i) The OR gate : It is a circuit with two or more inputs and one output in which the output signal is HIGH if any one or more of the inputs is HIGH.
The OR operation represents a logical addition.
Below figure shows the 2-input OR gate logic sym-bol, and the Boolean expression and the truth table for the OR function.

(ii) The AND gate : It is a circuit with two or more inputs and one output in which the output signal is HIGH if and only if all the inputs are HIGH simultaneously.

The AND operation represents a logical multiplication.

Below figure shows the 2-input AND gate logic symbol and the Boolean expression and the truth table for the AND function.
Logic symbol:

Truth table:

Boolean expression:
Y = A ∙ B

(iii) The NAND gate : It is a circuit with two or more inputs and one output, whose output is HIGH if any one or more of the inputs is LOW; the output is LOW if all the inputs are HIGH.

The NAND gate is a combination of an AND gate followed by a NOT gate so that the truth table of the NAND function is obtained by inverting the outputs of the AND gate.

Question 15.
Why is the emitter, the base and the collector of a BJT doped differently?
Answer:
A BJT being a bipolar device, both electrons and holes participate in the conduction process. Under the forward-biased condition, the majority carriers injected from the emitter into the base constitute the largest current component in a BJT. For these carriers to diffuse across the base region with t negligible recombination and reach the collector junction, these must overwhelm the majority carriers of opposite charge in the base. The total emitter current has two components, that due to majority carriers in the emitter and that due to minority carriers diffused from base into emitter. The ratio of the current component due to the injected majority carriers from the emitter to the total emitter current is a measure of the emitter efficiency. To improve the emitter efficiency and the common-base current gain (a), it can be shown that’ the emitter should be much heavily doped than the base.

Also, the base width is a function of the base- collector voltage. A low doping level of the collector increases the size of the depletion region. This increases the maximum collector-base voltage and reduces the base width. Further, the large depletion region at the collector-base junction-extending mainly into the collector-corresponds to a smaller electric field and avoids avalanche breakdown of the reverse-biased collector-base junction.
[Note : Effective dopant concentrations of (a) npn transistor (b) pnp transistor are shown below.

The base doping is less than the emitter doping but greater than the collector doping. Contrary to the impression stressed in the Board’s and NCERT textbooks, collector doping is typically an order of magnitude lower than base doping. {Ref. : Semiconductor Devices Physics and Technology (3rd Edition), Simon M. Sze and M. K. Lee, p. 125}]

Question 16.
Which method of biasing is used for operating transistor as an amplifier?
Answer:
For use as an amplifier, the transistor should be in active mode. Therefore, the emitter-base junction is forward biased and the collector-base junction is reverse biased. Also, an amplifier uses an emitter bias rather than a base bias.

Question 17.
Define α and β. Derive the relation between then.
Answer:
The dc common-base current ratio or current gain (α_dc) is defined as the ratio of the collector current to emitter current.
α_dc = \(\frac{I_{C}}{I_{\mathrm{E}}}\)
The dc common-emitter current ratio or current gain (β_dc) is defined as the ratio of the collector current to base current.
β_dc = \(\frac{I_{C}}{I_{B}}\)
Since the emitter current I_E = I_B + I_C
\(\frac{I_{\mathrm{E}}}{I_{C}}=\frac{I_{\mathrm{B}}}{I_{\mathrm{C}}}+1\)
∴ \(\frac{1}{\alpha_{\mathrm{dc}}}=\frac{1}{\beta_{\mathrm{dc}}}+1\)
Therefore, the common-base current gain in terms of the common-emitter current gain is
α_dc = \(\frac{\beta_{\mathrm{dc}}}{1+\beta_{\mathrm{dc}}}\)
and the common-emitter current gain in terms of the common-base current gain is
β_dc = \(\frac{\alpha_{\mathrm{dc}}}{1-\alpha_{\mathrm{dc}}}\)
For a transistor, α_dc is close to but always less than 1 (about 0.92 to 0.98) and β_dc ranges from 20 to 200 for most general purpose transistors.

Question 18.
The common-base DC current gain of a transistor is 0.967. If the emitter current is 10mA. What is the value of base current?
Answer:
Data : α_dc = 0.967, I_E = 10 mA
α_dc = \(\frac{I_{C}}{I_{\mathrm{E}}}\) and I_E = I_B + I_C
The collector current,
I_C = α_dcI_E = 0.967 × 10 = 9.67 mA
Therefore, the base current,
I_B = I_E – I_C = 10 – 9.67 = 0.33 mA

Question 19.
In a comman-base connection, a certain transistor has an emitter current of 10mA and collector current of 9.8 mA. Calculate the value of the base current.
Answer:
DATA : I_E = 10 mA, I_C = 9.8 mA
I_E = I_B + I_C
Therefore, the base current,
I_B = I_E – I_C – 10 – 9.8 = 0.2 mA

Question 20.
In a common-base connection, the emitter current is 6.28mA and collector current is 6.20 mA. Determine the common base DC current gain.
Answer:
Data : I_E = 6.28 mA, I_C = 6.20 mA
α_dc = \(\frac{I_{C}}{I_{\mathrm{E}}}\) and β_dc = \(\frac{I_{\mathrm{C}}}{I_{\mathrm{B}}}=\frac{\alpha_{\mathrm{dc}}}{1-\alpha_{\mathrm{dc}}}\)
Common-emitter current gain, α_dc = \(\frac{6.20}{6.28}\) = 0.9873
Therefore, common-base current gain,
β_dc = \(\frac{0.9873}{1-0.9873}=\frac{0.9873}{0.0127}\) = 77.74
OR
I_E = I_B + I_C
∴ I_B = I_E – I_C = 6.28 – 6.20 = 0.08 mA
∴ β_dc = \(\frac{6.20}{0.08}\) = 77.5
[Note : The answer given in the textbook obviously refers to the common-emitter current gain.]

12th Physics Digest Chapter 16 Semiconductor Devices Intext Questions and Answers

Remember this (Textbook Page No. 346)

Question 1.
A full wave rectifier utilises both half cycles of AC input voltage to produce the DC output.
Answer:
A half-wave rectifier rectifies only one half of each cycle of the input ac wave while a full-wave rectifier rectifies both the halves. Hence the pulsating dc output voltage of a half-wave rectifier has the same frequency as the input but that of a full-wave rectifier has double the frequency of the ac input.

Do you know (Textbook Page No. 346)

Question 1.
The maximum efficiency of a full wave rectifier is 81.2% and the maximum efficiency of a half wave rectifier is 40.6%. It is observed that the maximum efficiency of a full wave rectifier is twice that of half wave rectifier.
Answer:
The ratio of dc power obtained at the output to the applied input ac power is known as rectifier efficiency. A half-wave rectifier can convert maximum 40.6% of ac power into dc power, and the remaining power of 59.4% is lost in the rectifier circuit. In fact, 50% power in the negative half cycle is not converted and the remaining 9.4% is lost in the circuit. Hence, a half wave rectifier efficiency is 40.6%. The maximum efficiency of a full-wave rectifier is 81.2%, i.e., twice that of a half-wave rectifier.

Do you know (Textbook Page No. 349)

Question 1.
The voltage stabilization is effective when there is a minimum Zener current. The Zener diode must be always operated within its breakdown region when there is a load connected in the circuit. Similarly, the supply voltage V_s must be greater than V_z.
Answer:
A Zener diode is operated in the breakdown region. There is a minimum Zener current, I_z, that places the desired operating point in the breakdown region. There is a maximum Zener current, I_zM, at which the power dissipation drives the junction temperature to the maximum allowed. Beyond that current the diode can be damaged. Hence, the supply voltage must be greater than V_z and the current-limiting resistor must limit the diode current to less than the rated maxi mum, I_zM.

Remember this (Textbook Page No. 350)

Question 1.
Zener effect occurs only if the diode is heavily doped, because when the depletion layer is thin, breakdown occurs at low reverse voltage and the field strength will be approximately 3 × 10⁷ V/m. It causes an increase in the flow of free carriers and increase in the reverse current.
Answer:
Zener breakdown occurs only in heavily doped pn junctions (doping concentrations for both p- and n-regions greater than 1018 cm3) and can take place only if the electric field in the depletion region of the reverse-biased junction is very high. It is found that the critical field at which tunneling becomes probable, i.e., at which Zener breakdown commences, is approximately 10⁶ V/cm. [“internal Field Emissiot at Narrow Silicon and Germanium PN-Junctions,” Phys. Rev., 118, 425 (1960).]

Can you tell (Textbook Page No. 350)

Question 1.
How does a cell phone charger produce a voltage of 5.0 V form the line voltage of 230V?
Answer:
A phone charger is usually a 5 V power supply. A 4-diode bridge input rectifier rectifies the ac mains voltage a provide a high voltage dc. A transistor chopper switches this on and off at high frequency. This stage is required because this high frequency allows the transformer to be smaller, lighter and much lower in cost.

A small transformer steps this down to a low voltage high-frequency ac. An output rectifier and filter convert this to low-voltage (5 V) dc and smooths out the ripple. A chopper controller provides a feedback to the chopper through an optoisohitor and adjusts the chopping cycle to maintain the output voltage at 5 V.

Question 2.
Why is a resistance connected in series with a Zener diode when used in a circuit?
Answer:
The I-V characteristics in the breakdown region of a Zener diode is almost vertical. That is, the current I_Z can rapidly increase at constant V_Z. To prevent damage due to excessive heating, the Zener current should not exceed the rated maximum current, I_ZM. Hence, a current-limiting resistor R_s is connected in series with the diode.

I_Z and the power dissipated in the Zener diode will be large for I _L = 0 (no-load condition) or when I_L is less than the rated maximum (when R_s is small and R_L is large). The current-limiting resistor R_s is so chosen that the Zener current does not exceed the rated maximum reverse current, I_ZM when there is no load or when the load is very high.
The rated maximum power of a Zener diode is
P_ZM = I_ZM = V_Z

At n-load condition, the current through R is I = I_ZM and the voltage drop across it is V – V_Z, where V is the unregulated source voltage. The diode current will be maximum when V is maxi mum at V_max and I = I_ZM. Then, the minimum value of the series resistance should be
R_{s, min} = \(\frac{V_{\max }-V_{\mathrm{Z}}}{I_{\mathrm{ZM}}}\)

Question 3.
The voltage across a Zener diode does not remain strictly constant with the changes in the Zener current. This is due to R_Z, the Zener impedance, or the internal resistance of the Zener diode. R_Z acts like a small resistance in series with the Zener. Changes in I_Z cause small changes in V_Z .
Answer:
The I-V characteristics of a Zener diode in the breakdown region is not strictly vertical. Its slope is 1/R_Z, where R_Z is the Zener impedance.

Can you know (Textbook Page No. 354)

Question 1.
What is the difference between a photo diode and a solar cell?
Answer:
Both are semiconductor photovoltaic devices. A photodiode is a reverse-biased pn-junction diode while a solar cell is an unbiased pn-junction diode. Photod iodes, however, are optimized for light detection while solar cells are optimized for energy conversion efficiency.

Question 2.
When the intensity of light incident on a photo diode increases, how is the reverse current affected?
Answer:
The photocurrent increases linearly with increasing illuminance, limited by the power dissipation of the photodiode.

Do you know (Textbook Page No. 355)

Question 1.
LED junction does not actually emit that much light so the epoxy resin body is constructed in such a way that the photons emitted by the junction are reflected away from the surrounding substrate base to which the diode is attached and are focused upwards through the domed top of the LED, which itself acts like a lens concentrating the light. This is why the emitted light appears to be brightest at the top of the LED.
Answer:
The pn-junction of an LED is encased in a transparent, hard plastic (epoxy resin), not only for shock protection but also for enhancing the brightness in one direction. Light emitted by the pn-junction is not directional. The hemispherical epoxy lens focuses the light in the direction of the hemispherical part. This is why the emitted light appears to be brightest at the top of the LED.

Question 2.
The current rating of LED is of a few tens of milli-amps. Hence it is necessary to connect a high resistance in series with it. The forward voltage drop of an LED is much larger than an ordinary diode and is around 1.5 to 3.5 volts.
Answer:
Most common LEDs require a forward operating voltage of between approximately 1.2 V (for a standard red LED) to 3.6 V (for a blue LED) with a forward current rating of about 10 mA to 30 mA, with 12 mA to 20 mA being the most common range. Like any diode, the forward current is approximately an exponential function of voltage and the forward resistance is very small. A small voltage change may result in a large change in current. If the current exceeds the rated maximum, an LED may overheat and get destroyed. LEDs are current driven devices and a current-limiting series resistor is required to prevent burning up the LED.

Do you know (Textbook Page No. 356)

Question 1.
White Light LEDs or White LED Lamps:
Shuji Nakamura, a Japanese – born American electronic engineer invented the blue LED. He was awarded the Nobel prize for physics for 2014. He was also awarded the global energy prize in the year 2015. His invention of blue LED made the fabrication of white LED possible.
LED lamps, bulbs, street lighting are becoming very popular these days because of the very high efficiency of LEDs in terms of light output per unit input power(in milliWatts), as compared to the incandescent bulbs. So for general purpose lightings, white light is preferred.
Commercially available white LEDs are normally manufactured by using the technique of wavelength conversion. It is a process which partly or completely converts the radiation of a LED into white light. There are many ways of wavelength conversion. One of these methods uses blue LED and yellow phosphor. In this method of wavelength conversion, a LED which emits blue colour is used to excite a yellow colour phosphor. This results in the emission of yellow and blue light and this mixture of blue and yellow light gives the appearance of white light. This method is the least expensive method for producing white light.
Answer:

The all important blue LEDs
The development of LEDs has made more efficient light sources possible. Creating white light that can be used for lighting requires a combination of red, green and blue light. Blue LEDs proved to be much more difficult to create than red and green LEDs. During the 1980s and 1990s Isamu Akasaki, Hiroshi Amano, and Shuji Nakamura successfully used the difficult-to-handle semiconductor gallium nitride to create efficient blue LEDs. Isamu Akasaki is known for invent ing the bright gallium nitride (CaN) pn-junction blue LED in 1989 and subsequently the high-brightness CaN blue LED.

Using blue LEDs, highly efficient white light sources. became possible by converting part of the blue light emitted from an LED to yellow using a phosphor. To the human eye, the combination of blue and yellow light is perceived as white. A white LED can be created by embedding phosphors in the plastic cap which surrounds a blue LED. Higher quality white light can also be created by mixing blue light with other colors as well, including red and green

Isamu Akasaki, together with Shuji Nakamura and Hiroshi Amano, received the 2014 Nobel Prize in Physics for the invention of efficient blue light-emitting diodes which has enabled bright and energy saving white light sources.

Use your brain power (Textbook Page No. 357)

Question 1.
What would happen if both junctions of a BJT are forward biased or reverse biased?
Answer:
A BJT has four regimes of operation, depending on the four combinations of the applied biases (voltage polarities) to the emitter-base junction and the collector-base junction, as shown in the following table; ‘F’ and ‘R’ indicate forward bias and reverse bias, respectively.

Remember This (Textbook Page No. 358)

Question 1.
The lightly doped, thin base region sandwiched between the heavily doped emitter region and the intermediate doped collector region plays a crucial role in the transistor action.
Answer:
If the two junctions in a BJT are physically close compared with the minority carrier diffusion length (i.e., the distance within which recombination will take place), the careers injected from the emitter can diffuse through the base to reach the base-collector junction. The narrow width of the base is thus crucial for transistor action.

Use your brain power (Textbook Page No. 361)

Question 1.
If a transistor amplifies power, explain why it is not used to generate power.
The term ‘amplification’ is used as an abstraction of the transistor properties so that we have few equations which are useful for a large number of practical problems. Transistors use a small power to control a power supply which can output a huge power. The large output comes from the power supply, while the input signal valves the transistor on and off. The increased power comes from the power supply so that a transistor does not violate the law of conservation of energy.

Maharashtra State Board Class 12 Textbook Solutions

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