How to proceed?

. . .
. .
. . .
. .
.
. . . .

System: That part of the universe in which observations are made

Surroundings: Rest of the universe

Boundary: Anything that separates systems and surroundings

 Types of System

Mass Exchange Energy Exchange

OPEN

CLOSED

ISOLATED

Open Closed
Example

Cup of tea Human Body Mobile Phone Laptop

 Equilibrium

An isolated system is in equilibrium when its macroscopic properties remain

constant with time.

Mechanical Equilibrium

Thermodynamic Equilibrium Material / Chemical Equilibrium

.. . . . Thermal Equilibrium
.
. . .. P
. . .
.. . . .T
.V.
 State of a System

It is the condition in which the system is present and it can be defined by

specifying some observable properties of the system.

State A State B

State Functions Path Functions

Properties that depend on state Quantities ( not properties ) not
of the system and not on the depend on the path followed by a
path followed to attain that state. system to achieve particular state.

Eg: U, T, P, V, H, G etc Eg: Work, Heat, heat capacities

 WI

WII
A > B

WIII
 Intensive and Extensive Properties

Intensive Properties Extensive Properties

Which don’t depend on amount or bulk Which depend on amount or bulk of
of matter. matter.
These are non-additive These are additive

Eg: T, P, Cm, density, Concentration, Eg: Mass, Volume, Internal energy,

refractive Index, V.P, Molar volume, molar Enthalpy, Gibbs energy, Entropy
energy, molar entropy, molar enthalpy,
molar mass

All specific & molar quantities are intensive.

Extensive Property
= Intensive Property
Mass
Zeroth law of Thermodynamics

A B A B

800 200
T = same in both thermal equilibrium

A B A B TA = TB
B C T B = TC
C A C TA = TC
Zeroth law of Thermodynamics

If two systems are separately in thermal equilibrium with a third system, then the
two systems are also in thermal equilibrium.

Temperature is an abstract property and it’s not measured directly

V ∝ T
Thermodynamic Process

Isothermal process

Isochoric process

Isobaric process

Adiabatic process
Thermodynamic Process
Thermodynamic Process
Thermodynamic Process
Thermodynamic Process

Irreversible process
Thermodynamic Process

Irreversible process
Thermodynamic Process

Reversible process
Thermodynamic Process

Reversible process
Modes of Energy Exchange

These are two ways by which a system can interact or can exchange energy
with its surroundings.

Heat Work

Heat: When the energy transfer takes place because of temperature difference
between system & surroundings. It is known as heat.
Modes of Energy Exchange
Modes of Energy Exchange

Work : Energy transfer which is not heat or which is not because of

temperature difference is called work.
 IUPAC Sign convention about Heat and Work

Work done on the Work done by the

system = +ve system = -ve
Example A system is provided 50 J of heat and work done on the system is 10 J.
What is the change in internal energy?
Example Which of the following pair shows extensive properties?

a) T and P
b) Viscosity & surface tension
c) Volume and internal energy
d) Refractive index & specific heat
Example For an isothermal process, the essential condition is

a) ΔT = 0
b) ΔH = 0
c) ΔU = 0
d) dT = 0
First Law of Thermodynamics (FLOT)
Law of Energy Conservation

Energy of total universe is always conserved.

or
Total energy of an isolated system is always conserved.
or
Hence absolute value of E can never be calculated only change in value of E
can be calculated for a particular process.
Internal Energy (E, also denoted by U)

Every system having some quantity of matter is associated with a definite

amount of energy, called internal energy .

If for a gas the internal energy is directly proportional to its absolute

temperature then the gas is termed as an ideal gas.
Example Which has maximum internal energy at 290K?

a) Ne (g)
b) N2 (g)
c) O3 (g)
d) Equal for all
Degree of freedom

The total no of modes on which a molecule of an ideal gas can exchange energy
during collisions is known as its degrees of freedom.
Degree of freedom
Heat Capacity

You know from everyday experience that the more you heat an object, the
higher its temperature, and the more you cool it, the lower its temperature.

Every object has its own heat capacity, the quantity of heat required to change
its temperature by 1 K.
 Heat Capacity

Heat Capacity

Total Heat Capacity Molar Heat Capacity Specific Heat Capacity

Heat required to raise the Heat required to raise the Heat required to raise the
temperature of given mass temperature of 1 mole by temperature of 1 gram by
by unit kelvin unit kelvin. unit kelvin.
Heat Capacity
Exampl
During an expansion of ideal gas the work done by gas is 100 J and the heat
e
capacity of process is found to be + 2 J/ºC. Find E of gas if the final temperature of
gas is 25ºC higher than its initial temperature.
Work Done

Energy that is transmitted from one system to another in such a way that
difference of temperature is not directly involved is known as work. It is a path
function.

Units
Heat & work both are forms of energy . Hence, their units are units of energy.
i.e.S system: Joules (J).
Much data is available in the old units of calories (cal) as well.
P × V = (litre. atmosphere) term which has unit of energy . It is useful to remember
the conversion
1 litre. atm = 101.3 Joules
 P - V Work

Assuming that under an external force Fx, the piston moves down by a distance ‘dx’.
Calculation of work for Isothermal expansion

Isothermal reversible expansion :

Calculation of work for Isothermal expansion

Isothermal reversible expansion :

Calculation of work for Isothermal expansion

Isothermal Irreversible expansion :

Calculation of work for Isothermal expansion

Isothermal reversible compression :

Calculation of work for Isothermal expansion

Isothermal Irreversible compression :

 Conclusion :

Whenever work is done on the gas then it will be minimum in case of reversible
process.
If expansion/compression takes place against constant external pressure then
it is irreversible.

If there is sudden change then the process is

irreversible.
Exampl
Calculate the work performed when 2 moles of hydrogen expand isothermally and
e
reversibly at 25ºC form 15 to 50 litres.
Exampl
If a gas at a pressure of 10 atm at 300 k expands against a constant external
e
pressure of 2 atm from a vol. of 10 litres to 20 litres find work done ?
Exampl A piston filled with 0.04 mol of an ideal gas expands reversibly from 50.0 mL to
e 375 mL at a constant temperature of 37.0°C. As it does so, it absorbs 208 J of
heat. The value of q and w for the process will be (R = 8.314 J mol −1 K−1)
(ln 7.5 = 2.01)
(JEE Main 2013)
a) q = −208 J, w = −208 J
b) q = −208 J, w = +208 J
c) q = +208 J, w = +208 J
d) q = +208 J, w = −208 J
Exampl Which of the following is correct option for free expansion of an ideal gas under
e adiabatic conditions?
a) q = 0, ΔT ≠ 0, w = 0
b) q ≠ 0, ΔT = 0, w = 0
c) q = 0, ΔT = 0, w = 0
d) q = 0, ΔT < 0, w ≠ 0
Calculation of Cp and Cv

I. Constant volume process (Isochoric)

Calculation of Cp and Cv

II. Constant pressure process (Isobaric)

Example A gas obeys the equation of state pV = nRT + nbp where b is a constant. If
n moles of the gas expand from V1 to V2 reversibly at a constant temperature T,
the work done is given by

(a) nRT ln[V2 - nb/V1 - nb]

(b) nRT ln[V2 - nb/V1 - nb]
(c) zero
(d) nRT ln[V1 - nb/V2 - nb]
Example The molar heat capacity of water in equilibrium with ice at constant pressure is
(a) negative
(b) zero
(c) infinity
(d) 40.45 kJ K-1 mol-1
Example Consider an ideal gas that occupies 2.50 dm3 at a pressure of 3.00 bar. If
the gas is compressed isothermally at a constant pressure p ext , so that the
final volume is 0.500 dm3, calculate the smallest possible value of pext and
the work done using pext.

(a) 20 bar and 100 J

(b) 15 bar and 750 J
(c) 30 bar and 150 J
(d) 10 bar and 375 J
Relation between Cp and Cv for an ideal gas
For Ideal gas
For Ideal gas
Example When 0.1 mol of a gas absorbs 41.75 J of heat at constant volume, the rise in
temperature that occurs is equal to 20 K. The gas must be
a) Triatomic
b) Diatomic
c) polyatomic
d) monoatomic
Example A steam boiler made up of steel weighs 900 kg. The boiler contains 400 kg of water.
Assuming 70% of the heat is delivered to boiler and water, how much heat
is required to raise the temperature of the whole from 10°C to 100°C?
Heat capacity of steel is 0.11 kcal kg−1 K−1 and heat capacity of water is
1 kcal kg−1 K−1.
a) 65321 kcal
b) 64157 kcal
c) 6869 kcal
d) 66549 kcal
 Enthalpy (H)

Most physical and chemical changes occur at nearly constant atmospheric

pressure — a reaction in an open flask, the freezing of a lake, a biochemical
process in an organism.

Enthalpy, a thermodynamic variable that relates directly to energy changes at

constant pressure.
Enthalpy (H)
Enthalpy (H)
Exothermic and Endothermic Processes

Because H is a combination of the three state functions E, P, and V, it is also a

state function. Therefore, ΔH equals
Comparing ΔE and ΔH

Knowing the enthalpy change of a system tells us a lot about its energy change as
well.

Reactions that do not involve gases.

Reactions in which the amount (mol) of gas does not change.

Reactions in which the amount (mol) of gas does change.

Example a) H2(g) + Cl2(g) → 2HCl (g) ; ΔH =
b) PCl5(g) → PCl3 (g) + Cl2 (g) ; ΔH =
c) CO(g) + O2(g) → CO2 (g) ; ΔH =
Example The difference between heats of reaction at constant pressure and constant volume
for the reaction :
2 C6H6(l) + 15O2(g) ⟶ 12CO2(g) + 6H2O(l) at 25ºC in kJ is
IIT - 1991
(a) –7.43 (b) +3.72
(c) –3.72 (d) +7.43
Example One mole of a non-ideal gas undergoes a change of state
(2.0 atm, 3.0L, 95(K) ⟶ (4.0 atm, 5.0 L, 245K) with a change in internal energy, ΔU
= 30.0 Latm. The change in enthalpy (ΔH) of the process in L atm is
IIT 2002
(a) 40.0
(b) 42.3
(c) 44.0
(d) not defined, because pressure is not constant
Example Two moles of an ideal gas is expanded isothermally and reversibly from 1 litre to 10
litre at 300 K. The enthalpy change (in kJ) for the process is

IIT 2004
(a) 11.4 kJ (b) – 11.4 kJ (c) 0 kJ (d) 4.8 kJ
Calorimetry: Measuring the Heat of a chemical or physical process

How do we know the heat of an acid-base reaction or the Calories in a teaspoon

of sugar?

Constant-Pressure Calorimetry: For

processes that take place at constant
pressure, the heat transferred (qP) is often
measured in a coffee-cup calorimeter
 Calorimetry: Bomb Calorimeter or Constant-Volume Calorimetry

Constant-volume calorimetry is carried out in a bomb calorimeter, a device commonly

used to measure the heat of combustion reactions, such as for fuels and foods.
Example 1g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1
atmospheric pressure according to the equation.
C (graphite) + O2 (g) → CO2 (g)
During the reaction, temperature rises from 298 k to 299 k. If the heat capacity of
the bomb calorimeter is 20.7kJ/K. What is the enthalpy change for the above
reaction at 298 K and 1 atm?
 Δ
Example For the reaction FeCO3 (s) ⟶ FeO(s) + CO2(g) ; ΔH = 80 KJ at 250C
What is ΔU at 250 C ?
Adiabatic Process
Example Derive PV𝛾= const. from TV𝛾-1 = constant
Calculation of work for Adiabatic Process

Reversible Adiabatic:
Calculation of work for Adiabatic Process

Irreversible Adiabatic:
Example What is the final temperature of 0.10 mol mono-atomic ideal gas that performs 75
cal. Of work adiabatically if the initial temperature is 2270C.

a) 250 K
b) 350 K
c) 150 K
d) 275 K
Example
Example
Example An ideal gas in a thermally insulated vessel at internal pressure = p1, volume = V1
and absolute temperature = T1 expands irreversibly against zero external pressure,
as shown in the below diagram. The nal internal pressure, volume and absolute
temperature of the gas are p2, V2 and T2, respectively. For this expansion,
Example During an adiabatic process, the pressure of gas is found to be proportional to the
cube of the absolute temperature. The ratio of CP/CV for the gas is
Comparison of Adiabatic Expansion
Example The reversible expansion of an ideal gas under adiabatic and isothermal conditions is
shown in the below gure. Which of the following statement(s) is (are) correct?
Example A liquid of volume of 100L and at the external pressure of 10 atm. The liquid is
confined inside an adiabatic bath. External pressure of the liquid is suddenly increased
to 100 atm and the liquid gets compressed by 1 L against this pressure then find,

a) Work
b) ΔU
c) ΔH
Example Two separate experiments were carried out involving adiabatic reversible expansion,
taking monoatomic gas in one case and a diatomic gas in the second case. In each
case, the initial temperature was Ti and expansion was from volume
V1 to volume V2. The nal temperatures attained were TM for monoatomic gas and TD
for diatomic gas. Then
a) TM = TD < Ti
b) TM < TD < Ti
c) TD > TM > Ti
d) T, < TM < Tf
Example Which of the following statements is not correct?
(a) Final temperature in reversible adiabatic expansion is greater than that in
irreversible adiabatic expansion.
(b) When heat is supplied to an ideal gas in isothermal process, kinetic energy of gas
remains constant.
(c) When an ideal gas is subjected to adiabatic expansion, it gets cooled.
(d) Entropy increases when an ideal gas expands isothermally.
Example What is the final temperature of 0.10 mol mono-atomic ideal gas that performs
75 cal. Of work adiabatically if the initial temperature is 2270C.

a) 250 K
b) 350 K
c) 150 K
d) 275 K
Example
Example
Example During an adiabatic process, the pressure of gas is found to be proportional to the
cube of the absolute temperature. The ratio of CP/CV for the gas is
Example An ideal gas in a thermally insulated vessel at internal pressure = p 1, volume = V1
and absolute temperature = T1 expands irreversibly against zero external pressure,
as shown in the below diagram. The nal internal pressure, volume and absolute
temperature of the gas are p2, V2 and T2, respectively. For this expansion,
Comparison of Adiabatic Expansion
Comparison of Adiabatic Compression
Example The reversible expansion of an ideal gas under adiabatic and isothermal conditions
is shown in the below gure. Which of the following statement(s) is (are) correct?
Example Two separate experiments were carried out involving adiabatic reversible
expansion, taking monoatomic gas in one case and a diatomic gas in the second
case. In each case, the initial temperature was T i and expansion was from volume
V1 to volume V2. The final temperatures attained were TM for monoatomic gas and
TD for diatomic gas. Then
a) TM = T D < Ti
b) TM < T D < Ti
c) TD > T M > Ti
d) Ti < T M < Tf
 2nd Law of thermodynamics

T1 T2

Hot Cold

No process is possible whose sole result is the transfer of heat from a cooler to a
hotter body. [Clausius statement of the second law]
 2nd Law of thermodynamics

No process is possible whose sole result is the absorption of heat from a reservoir
and the conversion of this heat into work. [Kelvin-Planck statement of the second
law]

State of entropy of the entire universe, as an isolated system, will always

increase over time.
 Spontaneity

The first law of thermodynamics tells us about the relationship between the heat
absorbed and the work performed on or by a system. It puts no restrictions on the
direction of heat flow.

However, the flow of heat is unidirectional from higher temperature to lower

temperature. In fact, all naturally occurring processes whether chemical or
physical will tend to proceed spontaneously in one direction only.

The first law failed to explain:

Neutralization, Melting of ice > 0°, Cooling of a hot body, Free expansion of a
gas, mixing of gases etc.
 Spontaneity

A large number of processes in nature proceed preferentially in one direction, for

example, diffusion of gas from higher to lower pressure, neutralization of acid by
base, a gas expanding to fill up the balloon, etc. Such processes which occur on
their own accord are called spontaneous processes.

A spontaneous process is an irreversible process and may only be reversed by

some external agency. - NCERT
Spontaneity

Under given conditions, if a change is spontaneous in one direction,

it is not spontaneous in the other.

The rate at which the spontaneous processes occur, range from very slow to
very fast.
Spontaneity

Under given conditions, if a change is spontaneous in one direction,

it is not spontaneous in the other.

The rate at which the spontaneous processes occur, range from very slow to
very fast.
 What drives a Spontaneous Change

Is decrease in enthalpy a criterion for spontaneity ?

Therefore, it becomes obvious that while decrease in enthalpy may be a

contributory factor for spontaneity, but it is not true for all cases.
 Entropy and spontaneity

Let us examine such a case in which ΔH = 0 i.e., there is no change in enthalpy,

but still the process is spontaneous.

We may now formulate another postulate: in an isolated system, there is always a

tendency for the systems’ energy to become more disordered or chaotic and this
could be a criterion for spontaneous change
Entropy, S

One can think of entropy as a measure of the degree of randomness or disorder in

the system. The greater the disorder in an isolated system, the higher is the
entropy.

Like enthalpy, entropy is a state function. It depends only on the state of the
system.
Entropy, S

Whenever heat is added to the system, it increases molecular motions causing

increased randomness in the system. Thus heat (q) has randomising influence on
the system.

Heat added to a system at lower temperature causes greater randomness than

when the same quantity of heat is added to it at higher temperature. This
suggests that the entropy change is inversely proportional to the temperature.
 Entropy, S

For a spontaneous process in an isolated system, entropy always increases ie.

Example Predict in which of the following, entropy increases/decreases :

a. A liquid crystallizes into a solid

b. Temperature of a crystalline solid is raised from 0 K to 15 K
c. 2NaHCO3 (s) → Na2CO3(s) + CO2(g)+ H2O(g)
d. H2(g) → 2H(g)
Example For oxidation of iron, 4Fe(s) + 3O2(g) → 2Fe2O3(s) entropy change is
- 549.4 JK-1 mol-1 at 298 K, why is the reaction spontaneous?
( ΔrHθ for this reaction is -1648 x 103 J mol-1 )
Entropy, S
Entropy calculation for an ideal gas
Entropy calculation for an ideal gas
Entropy calculation for an ideal gas
Entropy calculation for an ideal gas
Entropy calculation for an ideal gas
Example The entropy change involved in the isothermal reversible expansion of 2 mol of an
ideal gas from a volume of 10 dm3 to a volume of 100 dm3 at 27°C is
(a) 35.8 J mol−1 K−1
(b) 32.3 J mol−1 K−1
(c) 42.3 J mol−1 K−1
(d) 38.3 J mol−1 K−1
(AIEEE 2011)
Example When one mole of an ideal gas is compressed to half of its initial volume and
simultaneously heated to twice its initial temperature, the change in entropy is
(a) CV ln 2 (b) Cp ln 2
(c) R ln 2 (d) (CV − R) ln 2
Example The entropy change can be calculated by using the expression S = Q rev/T. When
water freezes in a glass beaker, choose the correct statement amongst the
following.
(a) ΔS (system) decrease but ΔS (surroundings) remains the same.
(b) ΔS (system) increase but ΔS (surroundings) decreases.
(c) ΔS (system) decrease but ΔS (surroundings) increases.
(d) ΔS (system) decrease and ΔS (surroundings) also decreases.
Example The entropy (S°) of the following substances is:
CH4(g) 186.2 J K−1 mol−1; O2(g) 205.0 J K−1 mol−1;
CO2(g) 213.6 J K−1 mol−1; H2O(l) 69.9 J K−1 mol−1
The entropy change (S°) for the reaction: CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(l) is

(a) −312.5 J K−1 mol−1

(b) −242.8 J K−1 mol−1
(c) −108.1 J K−1 mol−1
(d) −37.6 J K−1 mol−1
Example The direct conversion of A to B is dicult; hence it is carried out by the following
shown path:

where eu is entropy unit, then ΔS(A → B) is

(a) +100 eu
(b) +60 eu
(c) −100 eu
(d) −60 eu (IIT-JEE 2006)
Example Statement 1: There is a natural asymmetry between converting work to heat and
converting heat to work.
Statement 2: No process is possible in which the sole result is the absorption of
heat from a reservoir and its complete conversion into work.

(a) Statement 1 is True. Statement 2 is True; Statement 2 is a

correct explanation for Statement 1.
(b) Statement 1 is True, Statement 2 is True; Statement 2 is
NOT a correct explanation for Statement 1.
(c) Statement 1 is True, Statement 2 is False.
(d) Statement 1 is False, Statement 2 is True. (IIT-JEE
2008)
Example Among the following, the intensive property is (properties are)
(a) molar conductivity.
(b) electromotive force.
(c) resistance.
(d) heat capacity. (IIT-JEE 2010)
Example When one mole of an ideal gas is compressed to half of its initial volume and
simultaneously heated to twice its initial temperature, the change in entropy is
(a) CV ln 2 (b) Cp ln 2
(c) R ln 2 (d) (CV − R) ln 2
Example The entropy change can be calculated by using the expression S = Q rev/T. When
water freezes in a glass beaker, choose the correct statement amongst the
following.
(a) ΔS (system) decrease but ΔS (surroundings) remains the same.
(b) ΔS (system) increase but ΔS (surroundings) decreases.
(c) ΔS (system) decrease but ΔS (surroundings) increases.
(d) ΔS (system) decrease and ΔS (surroundings) also decreases.
Example The entropy (S°) of the following substances is:
CH4(g) 186.2 J K−1 mol−1; O2(g) 205.0 J K−1 mol−1;
CO2(g) 213.6 J K−1 mol−1; H2O(l) 69.9 J K−1 mol−1
The entropy change (ΔS°) for the reaction: CH4(g) + 2O2(g) ⟶ CO2(g) + 2H2O(l) is

(a) −312.5 J K−1 mol−1

(b) −242.8 J K−1 mol−1
(c) −108.1 J K−1 mol−1
(d) −37.6 J K−1 mol−1
Example The direct conversion of A to B is dicult; hence it is carried out by the following
shown path:

where eu is entropy unit, then ΔS(A → B) is

(a) +100 eu
(b) +60 eu
(c) −100 eu
(d) −60 eu (IIT-JEE 2006)
Example Statement 1: There is a natural asymmetry between converting work to heat and
converting heat to work.
Statement 2: No process is possible in which the sole result is the absorption of
heat from a reservoir and its complete conversion into work.

(a) Statement 1 is True. Statement 2 is True; Statement 2 is a correct explanation

for Statement 1.
(b) Statement 1 is True, Statement 2 is True; Statement 2 is NOT a correct
explanation for Statement 1.
(c) Statement 1 is True, Statement 2 is False.
(d) Statement 1 is False, Statement 2 is True. (IIT-JEE
2008)
Example Among the following, the intensive property is (properties are)
(a) molar conductivity.
(b) electromotive force.
(c) resistance.
(d) heat capacity. (IIT-JEE 2010)
Example A sample of argon gas at 1 atm pressure and 27°C expands reversibly and
adiabatically from 1.25 dm3 to 2.50 dm3. Calculate the enthalpy change in this
process. CV for argon is 12.48 JK–1 mol–1. IIT
2000
Example
Example For an ideal gas, consider only p−V work in going from an initial state X to the final
state Z. The final state Z can be reached by either of the two paths shown in the
below gure. Which of the following choice(s) is(are) correct? [Take ΔS as change in
entropy and w as work done.]
Example For the process H2O(l) ⟶ H2O(g) at T = 100°C and 1 atmosphere pressure, the
correct choice is
Example
Combining 1st and 2nd Law
Third Law of Thermodynamics

The Third Law allows us to define absolute entropies of substances and to define
the standard entropy of a reaction.

“The entropy of perfect crystals of all pure elements & compounds is zero at the
absolute zero of temperature.”

As far as thermodynamics is concerned, choosing this common value as zero is a

matter of convenience. The molecular interpretation of entropy, however, justifies
the value S = 0 at T = 0.
Third Law of Thermodynamics

Thus absolute value of entropy (unlike the absolute value of enthalpy) for any
pure substance can be calculated at any given temperature . In standard state
(298 K, 1 atm), it is standard absolute entropy Sº .
Gibbs Energy and Spontaneity
A system parameter to predict the spontaneity of chemical reaction was introduced
by Gibbs so that entropy calculation for the surrounding need not be carried out.
Gibbs Energy and Spontaneity
A system parameter to predict the spontaneity of chemical reaction was introduced
by Gibbs so that entropy calculation for the surrounding need not be carried out.
Gibbs Energy and Spontaneity
Gibbs energy change and equilibrium

Knowledge of ΔG of a chemical reaction allows:

● Prediction of the spontaneity of the reaction

● Prediction of the useful work that could be extracted from it
Example
Effect of temperature on spontaneity of reaction

ΔH ΔS ΔG
Example For a particular reversible reaction at temperature T, ΔH and ΔS were found to be
both positive. If Te is the temperature at equilibrium, the reaction would be
spontaneous when
(a) T = Te
(b) Te > T
(c) T > Te
(d) Te = 5T
(AIEEE 2010)
Example Identify the correct statement regarding a spontaneous process:
(a) Lowering of energy in the reaction process is the only criterion for spontaneity.
(b) For a spontaneous process in an isolated system, the change in entropy is
positive.
(c) Endothermic processes are never spontaneous.
(d) Exothermic processes are always spontaneous. (AIEEE
2007)
Gibbs Energy
Example Match the thermodynamic processes given under Column I with the expressions
given in Column II
Example
Example Select the correct set of statement/s :
1: Work done by the surrounding in case of infinite stage expansion is more than
single stage expansion
2: Irreversible work is always greater than reversible work. (with sign)
3: On an ideal gas in case of single stage expansion and compression system as
well as surrounding are restored back to their original states
4: If gas is in thermodynamic equilibrium is taken from state A to state B, by four
successive single stage expansions. Then we can plot 4 points on the P-V indicator
diagram.
(A) 2
(B) 1, 2, 3, 4
(C) 2, 4
(D) 1, 2, 4
Thermochemistry

The study of energy or heat changes accompanying a chemical reaction or a

physical change is called thermochemistry.