CHEMISTRY (CY11003)

Autumn 2020 -2021

LECTURE – 3
7th December 2020

Department of Chemistry,
Indian Institute of Technology Kharagpur
Thermodynamics:
■ It is the science of (i) heat and temperature, and (ii) the laws
that govern the conversion of thermal energy into mechanical,
or other forms of energy
■It is a macroscopic science and is not based on any molecular
model (Quantum mechanics);

■ Equations derived from laws of thermodynamics do not

provide us with the molecular interpretation of complex
phenomena;

■ Thermodynamics helps us predict the direction and extent of

chemical reactions;

■ It tells us nothing about the rate of a process (Kinetics)

Department of Chemistry,
Indian Institute of Technology Kharagpur
Some Basic Definitions:

■System: Any part of the universe in which we

have a special interest

■ Surroundings: The region outside the system

where we make our measurements

■ Boundary: A hypothetical/real barrier between

system and surroundings

 Universe: System + Surroundings

Some Basic Definitions (contd):
■ Homogeneous system: A system having its properties uniform
throughout (i.e., a single-phase system, e.g., pure substance or its
solution)

■ Heterogeneous system: A system with more than one phase, e.g.,

two immiscible liquids, a solid in contact with its saturated solution;

■ Open system: a system with boundary through which both mass and
energy can be exchanged with the surroundings;

■ Closed system: a system that can exchange energy but cannot

exchange mass with its surroundings;

■ Isolated system: a system that can neither exchange mass nor

energy with its surroundings;
■Intensive properties: that do not depend on size (the quantity of
matter present) of the system at all e.g., P, T, η, ρ, etc.
■ Extensive properties: that depend on size of the system e.g., m, V,
surface area (A), no. of moles (n), etc.

 Intensive property = ratio of two extensive properties;

Pressure (P) = Force/Area; Density (ρ) = Mass/Volume

Molar Volume (Vm) = V/n;

How do we Define a System or State of a System?

Thermodynamic System is at Equilibrium – Properties do not

change with time; No fluxes (no heat flowing through the system)

Macroscopic state of a system can be specified by the values of a small

number of macroscopic variables – Properties/Parameters
/Thermodynamic variables of the system

Thermodynamic state of a system of a pure substance of fixed amount

can be described by two of the three state variables (P, V, and T)

Microscopic state of a system needs description about each molecules –

a very complicated picture

Thermodynamic state is only defined by the present values of the

state variables, not by the history
What is Temperature?
■ is a measure of coldness or hotness;

Container of Gas A: PA, VA

Container of Gas B: PB, VB

■ Zeroth Law of Thermodynamics:

If two systems are in thermal
equilibrium with a third system, they
must also be in thermal equilibrium
with each other

T / K = t / ºC + 273.15
Heat:

■ Heat is the energy (q) transferred between two bodies that

are at different temperatures;

Heat is not a property of the system and is not a state function

■ Work and heat are not functions of state;

■ Changes in these quantities are path dependent;
The First Law of Thermodynamics:
■ Energy can be converted from one form to another
but cannot be created or destroyed

Euniv = Esys + Esurr ∆Euniv = ∆Esys + ∆Esurr = 0

∆Esys = – ∆Esurr

Etot = KE + PE + U U is Internal Energy = Etrans + Erot + Evib

Since the system is at rest, KE = 0 U differs from q and w in that it
And it is not under any force field, PE = 0 always changes by the same amount
in going from one state to another
Etot = U ∆U = U2 – U1
∆U = q + w First Law
dU = dq + dw ᵭq and ᵭw are NOT perfect (or
dU = ᵭq + ᵭw exact) differentials
Internal Energy (Contd.) ∆U = q + w
∆T α q ∆U = q − P∆V dU = dq − PdV
∆T = (1/C) q
■ Constant volume process: ∆V = 0, w = 0
C = q/∆T
∆U = qV or dU = dqV
CV = qV / ∆T
■ Expansion against vacuum: Pex = 0,
CV = ∆UV /∆T
w = 0, ∆U = q
CV = (dU / dT)V
■ For adiabatic changes, q = 0,
CV = n CV,m
∆U = − P∆V or dU = − PdV;
CV,m = (dUm / dT)V
■ For isothermal changes
dU = 0 => qT = − w = PdV
dUm = CV,m dT
 Heat Capacity of Gases:
Monatomic gases: Diatomic gases:

CV, m = 3/2 R ; CP, m = 5/2 R CV, m = 7/2 R ; CP, m = 9/2 R

γ = CP, m /CV, m = 5/3 = 1.67 γ = CP, m /CV, m = 9/7 = 1.29

Equipartition of Energy: For a mechanical system of N particles, 3N

degrees of freedom
If N particles are bound together to form polyatomic molecule,

Translational: Etrans = 1/2(m u2)+ 1/2(m v2)+ 1/2(m w2)

Rotational:
Erot = 1/2(I ωx2 ) + 1/2(I ωy2 ) (linear molecules, Ix = Iy = I)

Erot = 1/2(I ωx2 ) + 1/2(I ωy2 ) + 1/2(I ωz2 ) (nonlinear molecules)

Vibrational: 3N – 5 (linear) and 3N – 6 (nonlinear) vibrational modes each having
energy, Evib = 1/2μ (dr/dt)2 + 1/2k (r – ro)2
Heat Capacity of Gases: Contd.
For Polyatomic gases:
Etot = 3/2kBT + 2/2kB T + (3N – 5)kBT (linear)

Etot = 3/2kBT + 3/2kBT + (3N – 6)kBT (nonlinear)

For a mole of monatomic gases: Um = 3/2RT ; R = NA kB

For a mole of polyatomic gases:
Etot = Um = 3/2RT + 2/2R T + (3N – 5)RT (linear)

Etot = Um = 3/2RT + 3/2RT + (3N – 6)RT (nonlinear)

For monatomic gases: Cv,m = 3/2R

For polyatomic gases:
CV,m ≡ (dUm / dT)V
Cv,m = 5/2R + (3N – 5)R (linear)

Cv,m = 3R + (3N – 6)R (nonlinear)

Equipartition of Energy:
Boltzman Distribution Law:

N2 /N1 = exp(−∆E/kBT)

∆Evib >> kBT, N2 < N1;

∆Erot < kBT, N2 ≈ N1
Enthalpy:
At constant pressure, Since P = P2 = P1
∆U = qP – P∆V
qP = (U2 + P2 V2 ) – (U1 + P1 V1)
U2 – U1 = qP – P(V2 – V1)
Let H ≡ U + PV
qP = U2 – U1 + P(V2 – V1)
qP = H2 – H1 = ∆H; ∆H = qP
qP = (U2 + PV2 ) – (U1 + PV1)

∆H = ∆U + ∆(PV) = ∆U + P∆V + V∆P + ∆P∆V

At constant pressure, ∆P = 0 => ∆H = ∆U + P∆V

dH = dU + PdV + VdP + dP dV = dU + PdV + VdP

At constant pressure, dP = 0 => dH = dU + PdV
Enthalpy and Heat Capacity:
U2 T2
Cv,m = qv /∆T ; dU = CV dT
∫U1
dU = Cv ∫ dT
T1

CP,m = qP /∆T or CP, m = dqP / dT

CP,m = (dHm / dT)P or dHm = CP, m dT ∆U = U 2 − U1 = Cv (T2 − T1 )

For ideal gas, Adiabatic, CV, m independent of T w = ∆U - q = Cv (T2 − T1 )

CP = total molar heat capacity at constant pressure = n CP,m

CP (T) = a + b T + c T2

H = U + P V = U + nRT (for ideal gas)

dH = dU + nRdT CP dT = CV dT + nRdT => CP – CV = n R
CP, m – CV, m = R
 Gas Expansion: Ideal Gas
Isothermal Expansion:
Δ T = 0 => Δ UT = 0 => qT = – w
∆H = ∆U + ∆(PV) = ∆U + nR ∆T = 0 => ∆HT = 0
Adiabatic Expansion: q = 0 => Δ U = w

Reversible Process:
dU = – Pin dV dU = – PdV = – (nRT/V) dV
dU/nT = – R/VdV => CV dT/nT = – (R/V) dV => CV,m dT/T = – R/VdV

CV,m dlnT = – R dlnV => CV,m ln (T2 / T1) = R ln (V1 / V2)

CV,m ln (T2 / T1) = (CP, m – CV, m ) ln (V1/V2) ln (T2 / T1) = (CP, m /CV, m – 1) ln (V1/V2)

γ = CP, m /CV,m (positive, >1) and V2 > V1 => T2 < T1

=> Temperature of a gas decreases in a reversible adiabatic expansion

ln (T2/T1) = (γ – 1) ln (V1/V2) => T2 / T1 = (V1 / V2)γ – 1 => P2 / P1 = (V1 / V2)γ

 Adiabatic Gas Expansion: Ideal Gas
q = 0 => Δ U = w

Reversible Process:
dU = – Pin dV Cv dT = – Pin dV

Cv (T2 – T1 ) = – Pin (V2 – V1 )

Irreversible Process:
w = – Pex Δ V; Δ U = Cv Δ T

Cv (T2 – T1 ) = – Pex (V2 – V1 )

Here T2 < T1 => Adiabatic cooling

Here Pex < Pin =>
Δ T is maximum in reversible
process
Δ H = CP Δ T
EXACT & INEXACT DIFFERENTIALS:

dz = M(x, y)dx + N(x, y)dy

dz is an exact (or perfect) differential, if

(i) (∂M/∂y)x = (∂N/∂x)y

2
(ii) ∫ 1 dz = z2 – z1 = ∆z

(iii) ∫ dz = 0, for a cyclic process

EXACT & INEXACT DIFFERENTIALS:(contd)

dz = (y2 + 3x) dx + ex dy

M(x, y) = (y2 + 3x); N(x, y) = ex

(∂M/∂y)x = [∂ (y2 + 3x) /∂y]x = 2y

(∂N/∂x)y = [∂ ex /∂x]y = ex
dz is NOT an exact differential
PARTIAL DERIVATIVES:

dP = (∂P/∂V)T dV + (∂P/∂T)V dT

For a van der Waals gas,

(∂P/∂V)T = – RT/(Vm – b)2 + 2a/ Vm3

(∂P/∂T)V = R/(Vm – b)

dP = [–RT/(Vm – b)2 +2a/ Vm3 ]dV +R/(Vm – b) dT

EXACT & INEXACT DIFFERENTIALS:(contd)

dP = [– RT/(Vm – b)2 + 2a/ Vm3 ]dV + R/(Vm – b) dT

[∂{–RT/(Vm – b)2 + 2a/ Vm3 }/∂T]V = – R/(Vm – b)2

[∂{R/(Vm – b)}/∂V]T = – R/(Vm – b)2

dP is an exact differential

Similarly dV is an exact differential

EXACT & INEXACT DIFFERENTIALS:(contd)
 ∂U   ∂U 
H = f ( P, T )
U (T, V) dU =   dV +  dT
 ∂V T  ∂T V  ∂H   ∂H 
dH =   dP +   dT
 ∂P T  ∂T  P
CV = (∂U/∂T)V CP = (∂H/∂T)P

dU = CV dT + (∂U/∂V)T dV dH = CP dT + (∂H/∂P)T dP

∂ CV /∂V= ∂[(∂U/∂T)V]∂V ∂ CP/∂P= ∂[(∂H/∂T)P]∂P

= ∂[(∂U/∂V)T]∂T = ∂[(∂H/∂P)T]∂T

∂[(∂U/∂V)T]∂T = ∂ CV /∂V ∂[(∂H/∂P)T]∂T = ∂ CP /∂P

dU is a perfect differential dH is a perfect differential

∫21 dH = H2 – H1 = ∆H
f
∫i
dU = U f − U i = ∆U

∫21 dq = q ≠ q2 – q1
f
∫i
dw =w≠ w f − wi
 How CP & CV are Related?

dU = dq + dw = dq – Pex dV; dU = CV dT + (∂U/∂V)T dV

dq – Pex dV = CV dT + (∂U/∂V)T dV dq = CV dT + (∂U/∂V)T dV + Pex dV

At constant pressure, P = Pex dqP = CV dT + (P + (∂U/∂V)T) dV

dqP = CP dT => CP dT = CV dT + (P + (∂U/∂V)T) dV

CP – CV = {P + (∂U/∂V)T)} (dV/dT)P => Applicable for any gas

1/V(dV/dT)P = α => CP – CV = {P + (∂U/∂V)T)}V α

For an ideal gas, (∂U/∂V)T) = 0 => CP – CV = P (dV/dT)P

CP – CV = P (nR/P) = nR
Home Work:
Show that for a real gas Show that for an ideal gas

(i) α = 1/T + (∂lnZ/∂T)P

(i)
(ii) κ = 1/P – (∂lnZ/∂P)T
 ∂P  α (ii)
(iii)   =
 ∂T V κ
α 2TV (iii)
(iv) C p − CV =
κ

(v)

(vi)
Thank you