First Law of

Thermodynamics
- problem solving approach
 Indirect
Direct
Expt.
Expt.
Evidences
Evidences

Rate of
rexn

Thermodynamics is the branch of science that describes the behaviour of matter and the transformation between
different forms of energy on a macroscopic scale

The molecular and macroscopic levels are related to each other by the branch of science called statistical
mechanics.
 System

Open Close Isolated

If a system can A closed system is Systems that can
exchange matter with one where no transfer exchange neither
the surroundings, it is of matter can occur matter nor energy
called an open between system and with the surroundings
system. surroundings. are called isolated
systems.

Q. A living cell is an example of –

A. Open system B. Close system C. Isolated system D. Close as well as isolated

Q. A sealed coca cola can is an example of –

A. Open system B. Close system C. Isolated system D. Close as well as isolated.
 What is difference between equilibrium and steady state ??
An isolated system is in equilibrium when its macroscopic properties remain constant with time.

A nonisolated system is in equilibrium when the following two conditions hold: (a) The system’s
macroscopic properties remain constant with time; (b) removal of the system from contact with its
surroundings causes no change in the properties of the system. If condition (a) holds but (b) does not
hold, the system is in a steady state.
Equilibrium

Mechanical Material Thermal

no unbalanced forces act on the concentrations of the there must be no
or within the system; hence chemical species in the change in the
the system undergoes no various parts of the properties of the
acceleration, and there is no system are constant in system or surroundings
turbulence within the time when they are
system separated by a
thermally conducting
wall
 Thermodynamic property :

Extensive Intensive
An extensive thermodynamic property An intensive thermodynamic property is
is one whose value is equal to the sum one whose value does not depend on the
of its values for the parts of the size of the system.
system.

Thermodynamic Processes:

Isobaric Isochoric Isothermal Adiabatic

∆P=0 ∆V=0 ∆T=0 ∆Q=0
 Reversible and Irreversible process :

A process carried out infinitesimally Slowly so that the driving force is only infinitesimally greater
than the opposing force , is called Reversible process.

Any process which does not take place in the above manner i;e a process which does not take place
infinitesimally slowly ,is said to be an Irreversible process.
IIT-JAM 2017
Work done in this cyclic process in which the direction of each process is
reversed, is ______ kJ.
 Internal energy :
In thermodynamics, the internal energy of a system is the energy contained within the system,
excluding the kinetic energy of motion of the system as a whole and the potential energy of the
system as a whole due to external force fields. It keeps account of the gains and losses of energy
of the system that are due to changes in its internal state.

Enthalpy :
To measure the energy changes that occur in chemical reactions, chemists usually use a related
thermodynamic quantity called enthalpy (H)The sum of a system’s internal energy E and the
product of its pressure P and volume V (from the Greek enthalpein, meaning “to warm”). The
enthalpy of a system is defined as the sum of its internal energy E plus the product of its
pressure P and volume V
H = E + PV
At constant pressure, the change in the enthalpy of a system is as follows:

dH = dE+d(PV) = dE+PdV+VdP = dE+PdV PV=nRT

ΔH = Δ(E+PV) = ΔE+ΔPV = ΔE+PΔV At constant pressure
ΔH = ΔE+PΔV = Q P +W – W = Q P PV1=n1RT and PV2=n2RT
Or, PΔV= ΔnRT
N.B:- For gaseous reaction ΔH = ΔE+ΔnRT
IIT-JAM 2013
IIT-JAM 2018
 Exact and Inexact Differentials

One issue in thermodynamics concerns whether the total differential of a multivariable function
(F=F(x,y) represents any two-variable function) is exact or inexact.
𝜕𝐹 𝜕𝐹
𝑑𝐹 = 𝑑𝑥 + 𝑑𝑦
𝜕𝑥 𝑦 𝜕𝑦 𝑥
𝑓
If dF is an exact differential, ‫ 𝐹𝑑 𝑖׬‬will be the same for all paths between the initial (xi, yi) and
𝑓
final (xf, yf) points, and the integral will be simply ‫ = 𝐹𝑑 𝑖׬‬Ff - Fi. Thermodynamic state functions,
like U and H, should have exact differentials.

Problem: If a function 𝑑𝐹 = 𝑥 2 + 𝑦 2 𝑑𝑥 + 2𝑥𝑦 𝑑𝑦 then show whether it is exact or not?

Soln:

The differential given below is an example of an exact differential.

𝑑𝐹 = 𝑥 2 + 𝑦 2 𝑑𝑥 + 2𝑥𝑦 𝑑𝑦
dF= Mdx + Ndy
𝜕𝐹 𝜕 𝜕𝐹
= 𝑥 2 + 𝑦2, = 2𝑦
𝜕𝑥 𝜕𝑦 𝜕𝑥
 𝜕𝐹 𝜕 𝜕𝐹
= 2𝑥𝑦 , = 2𝑦
𝜕𝑦 𝜕𝑥 𝜕𝑦
The differential given below is an example of an inexact differential.
𝑑𝐹 = 𝑥 2 + 𝑦 2 𝑑𝑥 − 2𝑥𝑦 𝑑𝑦
𝜕𝐹 2 2
𝜕 𝜕𝐹
=𝑥 +𝑦 , = 2𝑦
𝜕𝑥 𝜕𝑦 𝜕𝑥
𝜕𝐹 𝜕 𝜕𝐹
= −2𝑥𝑦 , = −2𝑦
𝜕𝑥 𝜕𝑥 𝜕𝑦
Work: Work in thermodynamics is defined as any quantity of energy that “flows” across the
boundary between the system and surroundings as a result of a force acting through a distance.

Heat: Heat is defined in thermodynamics as the quantity of energy that flows across the
boundary between the system and surroundings because of a temperature difference between the
system and the surroundings.
An infinitesimal amount of heat flow into or out of a system can be related to a change in temperature
by
dQ=CP dT

where CP is the heat capacity and has the definition

CP=∂q/∂T
Heat Capacity - C: Q = C dT Specific Heat Capacity (c): dQ = m c dT

The Ratio of Specific Heat is expressed as

γ=cp/cv
Q. Choose the correct statement(s) about heat capacity.
A. Molar heat capacity is an extensive property.
B. For solids molar heat capacity at constant pressure rises rapidly with temperature.
C. For gases 𝐶𝑝,𝑚 > 𝐶𝑣,𝑚
D. For liquids and solids the difference between 𝐶𝑝,𝑚 and 𝐶𝑣,𝑚 is much smaller compared to
gases.
Zeroth law of thermodynamics: Two systems that are separately in thermal equilibrium with a third
system are also in thermal equilibrium with one another.

Heat and Work :

1st law of thermodynamics: The internal energy U of an isolated system is constant.

There are two main methods energy can be transferred to or from a system. These are suggested
in the previous statement of the first law of thermodynamics. Mathematically, we can restate the
first law as
ΔEsys = Q + W
Or dU = dQ+dW
Q. A heating coil is immersed in a 100.0 𝑔 sample of water liquid which boils at 99.61°𝐶 in an
open insulated beaker on a laboratory bench at 1 𝑏𝑎𝑟 pressure. In this process, 10.0% of the
liquid is converted to the gaseous form at a pressure of 1 𝑏𝑎𝑟. A current of 2.00 𝐴 flows through
the heater from a 12.0 𝑉 battery for 1000 𝑠 to effect the transformation. The densities of
liquid and gaseous water under these conditions are 997 and 0.590 𝑘𝑔 𝑚−3 , respectively. The
internal energy change (in kJ) in this whole process is___ .
HCU 2016
 Reversible Isothermal Process

Work Done in Reversible Isothermal Expansion of Ideal Gas :

Graphical Method :

The isotherm PQ for the process is shown in below figure.

The net work done to expand the gas from a volume V1 to volume V2 will be, W = Area ABDC

Thus, area occupied below the curve in between AB and CD gives the required value of work done.
Analytical Method:

Analytically, we can be calculated by integrating dW between the limits V1 to V2.

𝑊 𝑉2
𝑊 = න 𝑑𝑊 = − න 𝑃𝑑𝑉
0 𝑉1

For a perfect gas, PV = nRT or P = nRT/V Substituting P =n RT/V in the above equation, we get,
𝑊 𝑉2
𝑛𝑅𝑇
𝑊 = න 𝑑𝑊 = − න 𝑑𝑉
0 𝑉1 𝑉
𝑉2 𝑉2
𝑊 = −𝑛𝑅𝑇 ln = −2.303 𝑛𝑅𝑇 log
𝑉1 𝑉1
𝑃1 𝑃1
𝑊 = −𝑛𝑅𝑇 ln = −2.303 𝑛𝑅𝑇 log
𝑃2 𝑃2

dU = Cv dT=0

dH = Cp dT=0

𝑄 𝑊 𝑉 𝑛𝑅𝑇 𝑉 𝑃
𝑄 = ‫׬‬0 𝑑𝑄 = − ‫׬‬0 𝑑𝑊 = ‫ 𝑉׬‬2 𝑑𝑉 = 𝑛𝑅𝑇 ln 𝑉2 = 𝑛𝑅𝑇 ln 𝑃1
1 𝑉 1 2
 Problems:
(1) Based on the principle of equipartition of energy, the molar heat capacity of CO2 at constant
volume Cv,m is
(A) 3.5R (B) 6R (C) 6.5R (D) 9R

Ans: Total degree of freedom for CO2 molecule is = 9 Out of which three translational and two
rotational mode and rest four are vibrational mode. So internal energy of this molecule is
1 1
U = 3 × 2 𝑘𝑇 + 2 × 2 𝑘𝑇 + 4 × 𝑘𝑇 = 6𝑘𝑇 So Cv,m = 6R

(2) One mole of a van der Waals gas undergoes reversible isothermal transformation from an initial
volume 𝑉1 to a final volume 𝑉2 . The expression for the work done is ---
𝑉 𝑉 −𝑏 1 1
(A) 𝑅𝑇 𝑙𝑛 𝑉2 + 𝑎 𝑉2 − 𝑉1 (B) −𝑅𝑇 𝑙𝑛 𝑉2−𝑏 + 𝑎 −𝑉
1 1 𝑉1 2
𝑃 𝑉 −𝑏 1 1
(C) 𝑅𝑇 𝑙𝑛 𝑃2 (D) 𝑅𝑇 𝑙𝑛 𝑉2 −𝑏 −𝑎 −𝑉
1 1 𝑉1 2

The work done by reversible isothermal process of real gas is

𝑉2 − 𝑏 1 1
𝑊 = 𝑅𝑇 𝑙𝑛 −𝑎 −
𝑉1 − 𝑏 𝑉1 𝑉2
(3) The enthalpy of vaporization ( ΔHvap ) is zero at
(A) Boyle temperature (B) critical temperature
(C) inversion temperature (D) boiling temperature

Ans : At critical temperature Enthalpy of vaporization is zero

(4) The standard enthalpy of formation ∆𝑓 𝐻300

0
at 1 bar and 300 K for the formation of 𝐶𝐹2 𝐶𝑙𝐶𝐹2 𝐶𝑙 (g)
from its constituent elements in the standard state is −900 kJ mol−1. Given R = 8.3 J K−1 mol−1, the
standard internal energy of formation ∆𝑓 𝑈300
0
at the same pressure and temperature is-
(A)−905 kJ mol−1 (B) −895 kJ mol−1 (C) 895 kJ mol−1 (D) 905 kJ mol−1

Ans: The formation of the given compound occurs by the reaction

2C(s) + 2𝐹2 (g)+𝐶𝑙2 (𝑔) → 𝐶𝐹2 𝐶𝑙𝐶𝐹2 𝐶𝑙 (g)
Here in this reaction ∆𝑛 = 1 − 2 − 1 = −2
Again we know ∆𝑓 𝐻300
0 0
= ∆𝑓 𝑈300 + ∆𝑛𝑅𝑇

Or, ∆𝑓 𝑈300
0 0
= ∆𝑓 𝐻300 − ∆𝑛𝑅𝑇 = −900000 kJ mol−1 –(-2∗ 8.314 ∗ 300) Jmol−1
0
∆𝑓 𝑈300 = −895011.6 J mol−1 ≅ −895 kJ mol−1
(6) The following reaction is carried out at 1 atm and 300 K
2𝐻2 (𝑔) + 𝑂2 (𝑔) → 2𝐻2 𝑂(𝑙)
∆𝑈 for the above reaction is 550 KJ, Assuming ideal gas behavior for 𝐻2 and 𝑂2 ,calculate the value
of ∆𝐻

Ans: We know ∆𝐻 = ∆𝑈 + ∆𝑛𝑅𝑇

So ∆𝐻 = 550000 𝐽 𝑚𝑜𝑙𝑒 −1 + (−3 × 8.314 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 × 300 𝐾)
∆𝐻 = 542.517 𝐽 𝑚𝑜𝑙𝑒 −1

IIT JAM 2015

(7) For an isothermal free expansion of an ideal gas into vacuum, which one of the following set of
values is correct?
(A) ΔU = 0, q > 0, w < 0 (B) ΔU > 0, q > 0, w = 0
(C) ΔU = 0, q = 0, w = 0 (D) ΔU < 0, q = 0, w < 0

Ans: Since it is isothermal process so ∆𝑇 = 0 ,again ∆𝑈 = 𝐶𝑣 ∆𝑇 = 0

For free expansion work done by the system is zero so w = 0
Again from First law of thermodynamics ∆𝑈 = 𝑄 + 𝑊 ,since both w and ∆𝑈 is zero so
Q=0

So correct option is (C)

 Work Done in Reversible Isothermal Compression of Ideal Gas :

Now suppose gas is compressed reversibly from volume V2 to V1. In this case, the external pressure
will be greater than pressure inside the cylinder by an infinitesimal amount dP. Thus external
pressure will be P+dP. Let the gas is compressed by an infinitesimal amount, say dV. The two
parameters pressure and volume are of opposite signs as during compression the pressure increases
and the volume decreases. Now the expression for the infinitesimal amount of work done on the
system by the surroundings is

𝑑𝑊 = − 𝑃 + 𝑑𝑃 𝑑𝑉 = −𝑃𝑑𝑉

Here the term dPdV is small quantity therefore it is ignored.

Let the gas is compressed from volume V2 to V1, then the work done (w’) by the surroundings on the
𝑉
gas is given by: 𝑊 ′ = − ‫ 𝑉׬‬2 𝑃𝑑𝑉
1
Taking the gas to be ideal ,thus substituting P=RT/V and P2 V2 = P1 V1 in the above expression we get
𝑉 𝑉 𝑃
𝑊 ′ = − ‫ 𝑉׬‬2 𝑃𝑑𝑉/𝑉 − 𝑅𝑇 ln 1 = −𝑅𝑇 ln 2
1 𝑉2 𝑃1
For n mole of gas the work done by the gas
𝑉1 𝑃2
𝑊′ = 𝑛𝑅𝑇 ln = 𝑛𝑅𝑇 ln
𝑉2 𝑃1
 Work done in Irreversible Isothermal Process

The work done by the gas can be proceeds via two ways
Expansion of gas irreversibly with external pressure Zero ( Free expansion)
Expansion of gas irreversibly with constant external pressure whose magnitude is less than the
pressure of the gas i;e 𝑃𝑒𝑥𝑡 < P
Free expansion :
𝑊 𝑊
𝑊 = − න 𝑑𝑊 = − න 𝑃𝑒𝑥𝑡 . 𝑑𝑉 = 0
0 0

Intermediate Expansion :

Let us consider the volume of the gas increases from V1 to V2 against constant external
pressure 𝑃𝑒𝑥𝑡 . Then the work done by the system is given by

𝑉2
𝑊 = − න 𝑃𝑒𝑥𝑡 . 𝑑𝑉 = −𝑃𝑒𝑥𝑡 (𝑉2 − 𝑉1 )
𝑉1

Since 𝑃𝑒𝑥𝑡 is less than P , the work done during intermediate isothermal expansion is numerically
less than the work done during reversible isothermal expansion in which 𝑃𝑒𝑥𝑡 is almost equal to
P.
Q. Choose the correct statement(s) about reversible and irreversible process-
A. Work done in an irreversible isothermal cycle is non zero.
B. 𝑤𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 ≥ 𝑤𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 is always true for any P-V work.
C. Under reversible condition maximum work can be extracted from a process between the same initial
and final states.
D. For a reversible cyclic process internal energy change is non zero.

For all thermodynamic

processes between the
same initial and final state,
the delivery of work is a
maximum for a reversible
Area under PV curve process.
gives work done. So,
here area under PV
curve is a rectangle
so, will find the area
of rectangle.
W=(V2​−V1​)(P2​−P1​)
 Reversible Adiabatic Expansion of Gas

Work done by the system :

From the first law of thermodynamics we know that ∆U = Q + W

For adiabatic process Q = 0 ,So W = ∆U = nCV . ∆T = nCV ( T2 − T1 )

Internal Energy Change :

𝜕U
We know : CV = 𝜕T V
: Or dU = CV dT
∆U = nCV . ∆T = nCV ( T2 − T1 )

Enthalpy Change :

The enthalpy of a system related with internal energy as

H = U + PV
Or, ∆H = ∆U + ∆ PV = ∆U + nR∆T
Again ∆U = nCV . ∆T

∆H = nCV . ∆T + nR∆T = n CV + R ∆T = nCP . ∆T

 Adiabatic Relationship :

𝜸−𝟏 𝜸 𝜸
𝜸
𝑷𝟏 𝑽𝟏 =
𝜸
𝑷𝟐 𝑽𝟐 𝑻𝟐 𝑽𝟏 𝑻𝟏 𝑷𝟐
= =
𝑻𝟏 𝑽𝟐 𝑻𝟐 𝑷𝟏

Irreversible Adiabatic Expansion of Gas

The work done by the gas can be proceeds via two ways

Expansion of gas irreversibly with external pressure Zero ( Free expansion)

Expansion of gas irreversibly with constant external pressure whose magnitude is less than the
pressure of the gas i;e 𝑃𝑒𝑥𝑡 < P

Free expansion : Since in a free expansion , the external pressure is zero , the work done W is also
zero . Internal energy change , which also equal wo W is zero. Since in an ideal gas , the internal
energy is a function of temperature , therefore ,if ∆U is zero so ∆T is also zero, it follows therefore
,that ∆H which is equal to ∆U + nR∆T, is also zero , thus in a free expansion ∆T = 0 ;W=0 and ∆H = 0
Intermediate Expansion :
Let us consider the volume of the gas increases from V1 to V2 against constant external pressure
𝑃𝑒𝑥𝑡 . Then the work done by the system is given by
𝑉2
𝑊 = − න 𝑃𝑒𝑥𝑡 . 𝑑𝑉 = −𝑃𝑒𝑥𝑡 (𝑉2 − 𝑉1 )
𝑉1

Further from the first law of thermodynamics in an adiabatic expansion

W = ∆U = nCV . ∆T = nCV ( T2 − T1 )

So from above two equation

𝑃𝑒𝑥𝑡 𝑉2 − 𝑉1 = − nCV ( T2 − T1 )
𝑅𝑇1 𝑅𝑇
nCV T2 − T1 = 𝑃𝑒𝑥𝑡 𝑉1 − 𝑉2 = 𝑃𝑒𝑥𝑡 ൗ𝑃 − 2ൗ𝑃
1 2
𝑻𝟏 𝑷𝟐 − 𝑻𝟐 𝑷𝟏 ൗ
𝑹𝑷𝒆𝒙𝒕 𝑷𝟏 𝑷𝟐
 Comparison of Isothermal Expansion and Adiabatic Expansion

For isothermal expansion For adiabatic expansion,

𝑉𝑓 𝑃𝑖 𝑉𝑓 𝑃𝑖
= =
𝑉𝑖 𝑃𝑖𝑠𝑜 𝑉𝑖 𝑃𝑎𝑑𝑖𝑎
As for expansion (𝑉𝑓 ) > (𝑉𝑖 ) and also for all gases γ > 1 , hence (Padia) < (Piso)

For Expansion: Wiso > Wadia For Compression: Wadia > Wiso
 Work done in Reversible Isobaric Process

For Isobaric process pressure is constant let pressure is 𝑃𝑒𝑥𝑡 for reversible process 𝑃𝑒𝑥𝑡 is
the pressure of the gas 𝑃2

Let us consider the volume of the gas increases from V1 to V2. Then the work done by the
system is given by
𝑉2
𝑊 = − න 𝑃𝑒𝑥𝑡 . 𝑑𝑉 = −𝑃2 (𝑉2 − 𝑉1 )
𝑉1

Work done in Irreversible Isobaric Process

𝑉2
𝑊 = − න 𝑃𝑒𝑥𝑡 . 𝑑𝑉 = −𝑃𝑒𝑥𝑡 (𝑉2 − 𝑉1 )
𝑉1
 Reversible Isothermal Expansion of Real Gas

The work done in the expansion of a gas is given by

dW = - PdV
V2
W = − න PdV
V1
For Van der Waal’s gas
an2
P+ 2 V − nb = nRT
V
nRT an2
P= − 2
V−b V
V2 V2 V2
nRT an2 nRT an2
−W=න + 2 dV = න dV − න 2 dV
V1 V − b V V1 V − b V1 V
V2 − nb 2
1 1
− W = nRT ln + an −
V1 − nb V2 V1
Internal Energy Change :

an2
For a van der waals gas , the term is the internal pressure of the gas .
V2
𝜕U
Further ,the quantity 𝜕V T
is also called internal pressure of tha gas.
𝜕U an2
= V2
𝜕V T
an2
dU = V2 dV
V dV 1 1
On integrating ‫ ׬‬dU = U2 − U1 = ∆U = ‫׬‬V 2 an2 V2 = − an2 −V
1 V2 1

Enthalpy Change :
1 1 1 1
∆H = ∆U + nRT − + an2 −
V2 − nb V1 − nb V2 V1

Heat Change :

V2 −nb
Q = nRT ln
V1 −nb
 Joule-Thomson Effect

𝜕T
𝜇𝐽𝑇 =
𝜕P H

Let us consider a volume of 𝑉1 of the gas enclosed between the piston A and the porus plug at a
pressure 𝑃1 is forced slowly through the porus plug by moving the piston A inward and is allowed to
expand to a volume 𝑉2 at a lower pressure 𝑃2 by moving the piston B outward ,as shown

Work done on the system at the piston A = +𝑃1 𝑉1

Work done by the system at the piston B = −𝑃2 𝑉2
Net work done by the system =+𝑃1 𝑉1 − 𝑃2 𝑉2
Since the expansion taken place adiabatically , the system is not in a
position to absorb heat from the surroundings. The system therefore ,
performs work at the expense of its internal energy. Consequently, the
internal energy of the system changes, say from 𝑈1 to 𝑈2 .

So , 𝑈2 − 𝑈1 = 𝑃1 𝑉1 − 𝑃2 𝑉2
Or , 𝑈2 + 𝑃2 𝑉2 = 𝑈1 + 𝑃1 𝑉1
Or , 𝐻2 = 𝐻1 ; ∆𝐻 = 0

𝜕T 1 𝜕H
𝜇𝐽𝑇 = =−
𝜕P H
𝐶𝑃 𝜕P 𝑇

1 𝜕H 1 𝜕V
𝜇𝐽𝑇 =− = T −𝑉
𝐶𝑃 𝜕P 𝑇
𝐶𝑃 𝜕T 𝑃

𝜇𝐽𝑇 = 0 for ideal gas. Joule-Thomson Coefficient for real gas

𝜕T 1 𝜕H
𝜇𝐽𝑇 = =−
𝜕P H 𝐶𝑃 𝜕P 𝑇
1 𝜕V 1 2𝑎
= T −𝑉 = −𝑏
𝐶𝑃 𝜕T 𝑃
𝐶𝑃 𝑅𝑇
 Inversion Temperature

The temperature at which 𝜇𝐽𝑇 become zero is known as inversion temperature.

𝜕T 1 2𝑎
𝜇𝐽𝑇 = =𝐶 −𝑏
𝜕P H 𝑃 𝑅𝑇 Temperature decrease
bcz the work of attractive
If 𝜇𝐽𝑇 is zero then 𝑇 = 𝑇𝑖 intramolecular forces
1 2𝑎
−𝑏 = 0 dominates
𝐶𝑃 𝑅𝑇 Increase of temperature
2𝑎
𝑇𝑖 = due to the work done by
𝑅𝑏 the repulsive interaction
Under experimental condition : of the gas is dominant
1 2𝑎 2𝑎
𝜇𝐽𝑇 is positive means 𝜇𝐽𝑇 > 0 ; 𝐶 −𝑏 >0; > 𝑇 ; 𝑇𝑖 > T
𝑃 𝑅𝑇 𝑅𝑏
Thus experimental temperature should be lesser than the inversion
temperature for cooling effect.
If 𝜇𝐽𝑇 is negative then 𝜕T should be positive , 𝑇2 > 𝑇1 , thus heating takes
place

Under experimental condition :

1 2𝑎 2𝑎
𝜇𝐽𝑇 is negative means 𝜇𝐽𝑇 < 0 ; 𝐶 −𝑏 <0 ; < 𝑇 ; 𝑇𝑖 < T
𝑃 𝑅𝑇 𝑅𝑏
Thus experimental temperature should be greater than the inversion
temperature for heating effect.
HCU 2016
IIT-JAM 2016
HCU 2016
 1
(8) The ∆𝐻0 for the reaction C𝑂(𝑔)+ 𝑂2(𝑔) → 𝐶𝑂2(𝑔) at 400 K in 𝑘𝐽𝑚𝑜𝑙𝑒 −1 is ---
2
------
∆𝐻𝑓0 (𝑘𝐽𝑚𝑜𝑙𝑒 −1 ) 𝐶𝑝0 (𝑘𝐽𝑚𝑜𝑙𝑒 −1 )
𝑂2 0 29.4
CO -110 29.1
𝐶𝑂2 -394 37.1
1
Ans : Here ∆𝐻0 = (∆𝐻𝑓0 (𝐶𝑂2 ) − ∆𝐻𝑓0 (𝐶𝑂) − ∆𝐻𝑓0 (𝑂2 )) + ∆𝐶𝑝0 × ∆𝑇
2
29.4
So ∆𝐻0 = (−394 − (−110) − 0) + (37.1 − 29.1 − )(400 − 298)
2

= −284 𝑘𝐽𝑚𝑜𝑙𝑒 −1
(10) At 298K and 1 atm, the molar enthalpies of combustion of cyclopropane and
propane are -2091 𝑘𝐽𝑚𝑜𝑙𝑒 −1 and -2058 𝑘𝐽𝑚𝑜𝑙𝑒 −1 , respectively. The enthalpy
change (𝑘𝐽𝑚𝑜𝑙𝑒 −1 ) for the conversion of one mole of propane to one mole of
cyclopropane is ---------
Ans : Propane → Cyclopropane
∆𝐻𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = 𝐻𝐶𝑦𝑐𝑙𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 − 𝐻𝑃𝑟𝑜𝑝𝑎𝑛𝑒
∆𝐻𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = −2091 − (−2058) 𝑘𝐽𝑚𝑜𝑙𝑒 −1 = 33 𝑘𝐽𝑚𝑜𝑙𝑒 −1
Things to remember:

• Basic concepts of system and surroundings

• Difference between steady state and equilibrium
• Intensive and extensive property
• State function and path function
• Concept of heat and work
• 1st law of thermodynamics ∆𝑈𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 = 0, ∆𝑈𝑠𝑦𝑠𝑡𝑒𝑚 = −∆𝑈𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 , ∆𝑈 = 𝑞 + 𝑤
• Concept of enthalpy
• Calculation of work and heat for different processes.
• Isothermal expansion and compression for ideal gas ∆𝐻 = ∆𝑈 = 0
• Reversible isothermal expansion and compression of ideal gas 𝑤 =
𝑉𝑓
− 𝑛𝑅𝑇𝑙𝑛 𝑉𝑖
• Irreversible isothermal expansion or compression
• Free expansion 𝑤 = 0
• Other than free expansion 𝑤 = −𝑃𝑒𝑥𝑡 𝑉𝑓 − 𝑉𝑖

• Adiabatic expansion or compression:

• ∆𝑈 = 𝑛𝐶𝑉 (𝑇𝑓 − 𝑇𝑖 ), ∆𝐻 = 𝑛𝐶𝑃 (𝑇𝑓 − 𝑇𝑖 )
• 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑦
• Comparison between isothermal and adiabatic expansion : 𝑃𝑖𝑠𝑜 >
𝑃𝑎𝑑𝑖 , starting from same initial pressure.