Thermodynamics

Kavya Agrawal
July 2022

1 Introduction
1. HEAT AND WORK

1.1 A system has energy, not heat/work.

1.2 Energy in transit form is called either heat or work.

1.3 Heat: Energy transferred due to temperature difference. Heat can be transferred via 3 methods:
-Conduction
-Convection
-Radiation

1.4 Light is electromagnetic radiation, or heat, a form of energy.

1.5 Work: Energy transferred due to some Force.

-PV-work: Piston
-Non-PV-work: Like gravitational or electrostatic field

2. ENERGY

2.1 There is no particular definition for ”energy”

2.2 The universe is made of energy and matter

2.3 Two forms:

-Kinetic: Due to motion (translational, rotational, vibrational)
-Potential: Due to force

2.4 Kinetic Energy of a system depends ONLY AND ONLY upon Temperature.

2.5 If two objects attract each other and then the distance between them is increased, potential energy increases ↑

2.6 For exothermic process at constant T: PE ↓

For endothermic process at constant T: PE ↑

1.1 Some basic definition or terms

1. System: Any macroscopic part of the universe under observation.
2. Surroundings: Remaining part of the universe other than the system is called surroundings.
Universe - System = Surroundings
NOTE: Change in properties of surroundings due to change in properties of system is negligible due to surroundings’ extremely
large size.
3. Boundary:
3.1 Anything that separates a system from its surroundings is known as a boundary.

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 3.2 Types of boundaries
3.2.1 Real or Imaginary
3.2.2 Rigid or Non Rigid
3.2.3 Adiabatic or Diathermal
3.2.4 Permeable or Non-permeable
3.3 Types of system depending upon type of boundaries
3.3.1 Isolated System: Neither energy nor matter can be exchanged
-Adiabatic, Rigid, Non-Permeable boundaries
-Ex. Thermos flask, Universe
3.3.2 Closed System: Which can transfer energy only
-Non-Permeable boundaries
-Ex. Balloon, Containers
3.3.3 Open System: Which can transfor matter (as well as energy)
-Permeable boundaries
-Ex. Open flask

4. Property: Anything that can be observed or measured about a system

4.1 Intensive Properties are mass independent, provided mass is changed by division of the system. Intensive properties’ values
do not change on dividing system.
4.2 Extensive properties’ values change on division of system.
4.3 An extensive property can be converted into intensive property by defining it per gram / per mole / per litre / etc.
4.4 Ratio of two extensive properties is intensive property.
4.5 Extensive properties are additive in nature, intensive properties are NOT additive.
4.6 Heat, Work re neither intensive nor extensive. They are not properties of a system!

2 State Function and Path Function

1. State Function: Function or property whose value depends only on final state and is independent of initial state and path used
to achieve final state. Ex. Latitude, Longitude

2. T (Temperature) is state function: Depends only on final state

ΔT (Change in Temperature) is Change in State Function: Depends on initial and final state but independent of path
3. Path Function: Depends on path. Ex. Heat, Work, Molar Heat Capacity

Essential criteria for a function to be a state function

4. AB dφ = φB – φA
R

H
5. dφ = 0
6. A state function must satisfy Euler’s Reciprocity Theorem.

φ = f(x, y)
"  #   
∂ ∂φ ∂ ∂φ
= (1)
∂y ∂x y ∂x ∂y x y
x

3 Change
1. A change can be Chemical Reaction, Phase change or Change in P,V,T, etc.
2. If Temperature is constant, P, V vary −→ Isothermal Process
If Volume is constant, P, T vary −→ Isochoric Process
If Pressure is constant, V, T vary −→ Isobaric Process
3. A Substance can be Ideal Gas, Real Gas or Solid|Liquid

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 3.1 Reversible and Irreversible change
4. Reversible Change
4.1 Which is carried out VERY SLOWLY
4.2 It takes ∞ steps and ∞ time to show any change
4.3 Reversible processes are hypothetical
4.4 Driving Force should be negligible / very small / infinitesimally small
4.5 System and Surroundings exist in the state of equilibrium throughout the process / change
4.6 Change in properties in each step should be negligible.
4.7 For ideal gas, PV = nRT can be used throughout the change.
5. Irreversible Process/Change
5.1 It takes finite time and finite steps to show any change.
5.2 It is practically feasible / it is not hypothetical
5.3 Driving force should be appreciable / considerable (not tends to zero)
5.4 System and Surroundings are in equilibrium only at initial and final state, not throughout.
5.5 Change in properties in each step should be appreciable / considerable / observable.
5.6 PV = nRT equation can be used only at initial and final states, not throughout.

4 Heat
1. Sign Convention: Heat given by the system represented as –ive (negative)
Heat given to the system represented as +ive (positive)
2. Upon giving heat to a system, it is not compulsary that temperature should change.
3. Molar Heat Capacity: Amount of heat required to raise the temperature by 1 Kelvin of 1 mole substance.
Represented by C.
Units −→ J/K/mol or Cal/K/mol
4. Specific Heat (S) −→ J/K/gm
5. Heat Capacity −→ J/K
R
6. Q = nCdT (not for chemical or phase change)
MHC (Molar Heat Capacity) of ice to water −→ Undefined
MHC of Isothermal −→ Unndefined

4.1 Characteristics of Molar Heat Capacity

6.1 As T ↑ C ↑; It is temperature dependent even for ideal gas
6.2 It is path/process dependent
At constant ’V’ = CV
At constant ’P’ = CP
For solids| liquids it is almost constant but for gases it changes appreciably
6.3 For an ideal gas CP = CV + R
6.4 For solids or liquids CP ≈ CV
6.5 For ideal gas, we can use degrees of freedom

Figure 1: Atomicity, Degrees of Freedom, MHC

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 6.6 Law of Equipartition: All D.O.F. receive equal part when KE increases.
nvib comes into play at very high temperature
At very low temperature (20K 30K) only ntr
 
ntr + nrot + 2nvib
CV = ·R (2)
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6.7 As atomicity ↑, CV ↑, CP ↑, γ ↓

5 Work
1. Sign Convention: Work done by the system is –ive (negative)
Work done on the system is +ive (positive)
R
2. W = – Pext dV
1 atm lit = 1.01325 × 105 Pa × 10–3 m3
= 101.325 J
1 bar lit = 100 J

3. W = 0 if V = constant (dV = 0) or Pext = 0 (Free Expansion)

6 Internal Energy
1. Energy due to system itself
Uint = UKE + UPE + Unuclear + Ue– + Umc2 (3)

2. Energy due to external factors like gravitational/magnetic/other forces are not considered.
3. Change in Internal Energy ΔU
ΔU = ΔUKE + ΔUPE + 0 + 0 + 0

4. For an ideal gas, no intermolecular foces, ΔU = 0

ΔUint = ΔUKE
U = f(T)

5. U = f(sub, n, P, V)
6. For a substance not undergoing any chemical or phase change
U = f(P, V) = f(P, T) = f(V, T) (4)

7. Taking U = f(V, T)
   
∂U ∂U
dU = dT + dV (5)
∂T V ∂V T
 
∂U
dU = CV dT + dV (6)
∂V T

8. Case-I For ideal gas undergoing any process

 
∂U
=0
∂V T
dU = nCV dT (7)

9. Case-II For real gas undergoing constant volume process

dV = 0
dU = nCV dT (8)

10. Case-III For solids and liquids undergoing any process

dV ≈ 0
dU = nCV dT = nCdT (9)

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7 First Law of Thermodynamics
1. Total Energy of the Universe is constant. (Energy can neither be created nor destroyed)
2. dU = q + w for a closed system

8 Enthalpy
1. Enthalpy is Enthalpy
2. H = U + PV
3. For a change at constant pressure dH = qp

4. Enthalpy is a state function

5. For a substance not undergoing any chemical and phase change

H = f(P, V) = f(P, T) = f(V, T) (10)

   
∂H ∂H
dH = dT + dP (11)
∂T P ∂P T
 
∂H
dH = CP dT + dP (12)
∂P T

6. Case-I For ideal gas undergoing any process

H = f(T)
 
∂H
=0
∂P T
dH = nCP dT (13)

7. Case-II For real gas undergoing constant pressure process

dP = 0
dH = nCP dT (14)

8. Case-III For solids and liquids undergoing any process

Change in pressure isn’t zero but change in properties of a solid or liquid due to change in pressure is negligible.
 
∂H
≈0
∂P T
dH = nCP dT = nCdT (15)

9. Relationship between ΔH and ΔU

9.1 ΔH = ΔU + Δ(PV)
9.2 Case-I For a substance not undergoing any chemical or phase change
9.2.1 For Ideal Gas

ΔH = ΔU + nRΔT (16)

9.2.2 For solid/liquid

ΔH ≈ ΔU (17)

9.3 Case-II For chemical and phase change

ΔH = ΔU + Δng RT (18)

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9 Calculation of q, w, ΔU, ΔH for various processes
9.1 Isothermal Process
1. dT = 0
2. ΔU = nCV dT = 0 (19)
3. ΔH = nCP dT = 0 (20)
4. From 1st law of thermodynamics: Q = –W

5. For Reversible Process

   
V2 P1
W = –nRTln = –nRTln (21)
V1 P2

6. For Irreversible Process

W = –Pext (V2 – V1 ) (22)

7. Conclusion

7.1 In case of expansion |Wrev | ≥ |Wirrev |

7.2 In case of compression |Wrev | ≤ |Wirrev |
7.3 In a reversible process, both system and surroundings can be restored to the original state simultaneously but in an
irreversible process both cannot be restored to their original state simultaneously.
7.4 Reversible processes are more efficient than Irreversible processes
7.5 Isothermal reversible and irreversible process end up at the same final state if carried ut against same final pressure from
same initial state.
8. Graphical Representation of Work Done
8.1 Expansion

Figure 2: Work Done in Isothermal Expansion

8.2 Compression

Figure 3: Work Done in Isothermal Compression

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9.2 Isochoric Process
1. V = constant, dV = 0
2. W = 0
3. From first law of thermodynamics (For all substance) Q = ΔU = nCV dT (23)
4. ΔH = nCP dT (For ideal gas, solid, liquid)
5. ΔH = ΔU + (P2 V2 – P1 V1 ) (For real gas)

9.3 Isobaric Process

1. P = constant, dP = 0
2. For all substance Q = ΔH = nCP ΔT
3. For ideal/solid/liquid ΔU = nCv ΔT
4. For real gas ΔH = ΔU + (P2 V2 – P1 V1 )
5. For any change and any substance W = –Pext (V2 – V1 )

6. Case-I For ideal gas not undergoing any chemical and phase change

W = –nRΔT (24)

7. Case-II For chemical and phase change

W = –Δng RT (25)

9.4 Adiabatic Process

1. Q = 0
2. W = ΔU = nCV ΔT
R
3. CV = γ–1
4. Work done
nR
W = ΔU = (T2 – T1 ) (26)
γ–1
1
W= [P2 V2 – P1 V1 ] (27)
γ–1

5. Change in Enthalpy

ΔH = nCP ΔT (28)
γ
ΔH = [P2 V2 – P1 V1 ] (29)
γ–1

6. On Expansion, V ↑, W < 0, ΔU < 0, ΔT < 0

Change in P ¿ Change in T
7. On Compression, V ↓, W > 0, ΔU > 0, ΔT > 0
Change in P ¿ Change in T
8. For reversible adiabatic process

TVγ–1 = constant (30)

PVγ = constant (31)
P1–γ Tγ = constant (32)

9. For irreversible adiabatic process

 
nRT2 nRT1
nCV (T2 – T1 ) = –Pext – (33)
P2 P1

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10. Conclusions
10.1 In case of expansion, |Wrev | ≥ |Wirrev |
10.2 In case of compression, |Wrev | ≤ |Wirrev |
10.3 Reversible process are more efficient than irreversible process
10.4 Upon compression, Vfinal,rev < Vfinal,irreversible
Tirrev > Trev (Always)
Adiabatic reversible and irreversible process do not end up at the same final state if carried out against same final pressure
from same initial state
10.5 All reversible process are Quasi-static (very slow) but all Quasi-static process are not reversible

11. Graphs
11.1 Case-I For same final pressure

Figure 4: Graph

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 11.2 Case-II For same final volume

Figure 5: Graph

11.3 Other

Figure 6: Graph

9.5 Polytropic Process

1. PVx = constant
2. Not all processes are polytropic. Ex. P = V + 3 or P = eV

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 3. Eq:
dP P
= –x (34)
dV V
nRΔT
W= (35)
x–1

4. MHC
R
C = CV – (36)
x–1

9.6 Cyclic Process

1. ΔUtotal = 0
2. ΔHtotal = 0
3. Qtotal = –Wtotal
4. |Wtotal | = Area enclosed in PV graph
5. Clockwise −→ W will be negative
Anticlockwise −→ W will be positive

Now that we know basics, we can start fun Thermodynamics with Entropy! (HAHAHAHAHA)

10 Entropy (S)
Path independent. S is state function.
q
dS = rev (37)
T

10.1 Carnot Cycle

AB = Isothermal Expansion
Q2 = –WAB = nRT2 ln (VB VA )
BC = Adiabatic Expansion
WBC = nCV (T1 – T2 )

CD = Isothermal Compression
Q1 = –WCD = nRT1 ln (VD VC )
DA = Adiabatic Compression
WDA = nCV (T2 – T1 )

–Wtotal
η = efficiency = × 100 (38)
Q2
Q + Q1
η= 2 × 100 (39)
Q2

For reversible carnot cycle

T2 – T 1
η= × 100 (40)
T2

10.2 Second Law of Thermodynamics

It is impossible for a cyclic process to cover heat into work without the simultaneous transfer of some part of heat from a body at
higher temperature to a body at lower temperature.

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10.3 Calculation of ΔS
1. Case-I For a substance not undergoing chemical/phase change
1.1 For ideal gas undergoing any process

  
T2 V2
ΔS = nCV ln + nRln (41)
T1 V1
   
T2 P1
ΔS = nCP ln + nRln (42)
T1 P2

1.2 For real gas

1.2.1 At constant volume
 
T2
ΔSsys = nCV ln (43)
T1

1.2.2 At constant pressure

 
T2
ΔSsys = nCP ln (44)
T1

1.3 For Solids/Liquids

 
T2
ΔSsys = nCln (45)
T1

10.4 Clausius Inequality

q
⋚ dS (46)
T

q
T < dS Irreversible
q
T = dS Reversible q ≤ TdS
q
T > dS Impossible
For an isolated system, eg. Universe
0 ≤ dS
Thus, Entropy of Universe CANNOT go down

ΔSsys + ΔSsurr ≥ 0 (47)

Adiabatic Reversible process is also known as Isoentropic. (ΔSsys = 0)

10.5 ΔS for Phase change

10.5.1 Boiling Point
There are two definitions of boiling point:
1. Temperature at which vapour pressure = external pressure
2. Temperature at which liquid and gas state exist in equilibrium
In fact, ”Boiling” is the wrong term.. We should use ”Evaporation”!
If substance is vaporising at boiling point, then it is Reversible. (Same for melting at melting point)

Qrev ΔH
ΔS = = (48)
T T

10.6 Physical Significance of Entropy

Order gives way to disorder spontaneously. More the number of options, more the uncertainty.
Uncertainty ↑, Disorder ↑, Occur spontaneously
Entropy ↑, Occur spoantaneously
Entropy is measure of disorder or randomness or uncertainty!

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10.7 Prediction of Sign of ΔSsys using the concept of randomness
10.7.1 With Temperature at constant ’V’

    0
>

T2 V2
ΔS = nCV ln + nR ln  (49)
T1 V1

As T ↑, ΔSsys > 0 Disorder ↑

10.7.2 With Volume at constant ’T’


 0  
>

T 2
 V2
ΔS = nCV ln  + nR ln (50)
T1 V1

As V ↑, ΔSsys > 0 Disorder ↑

10.7.3 Phase change

solid −→ liquid −→ gas

s < l << g
 
ΔH
Same result with
T

ΔSs and Sl can be neglected w.r.t. ΔSg

10.7.4 For chemical Reaction

Δng > 0 ΔSsys > 0

Δng < 0 ΔSsys = 0
Δng = 0 ΔSsys ̸= 0

10.7.5 Changing atomicity

Where Atomicity ↑ degree of freedom ↑ uncertainty ↑ disorder ↑
Thus, As Atomicity ↑ Entropy ↑

10.7.6 Same atomicity, Different Mass

For molecules having same atomicity, entropy increases as molecular mass increases. ex. N2 < O2

11 Third Law of Thermodynamics

At ‘0K’ (absolute zero temperature), entropy of a perfect crystal is zero.

11.1 Application of Third Law of Thermodynamics

11.1.1 To determine entropy of a substance given temperature and pressure
Substance (0K, P) → Substance (T1 , P1 )

R TMP dT ΔHfusion
ST = Cs+
R 0 T TMP
TBP dT ΔH vap (51)
+ Cl +
R TMP T TBP
T1 dT
+ Cp
TBP T

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11.1.2 To determine ΔSr
X X
ΔSr = S(Product) – S(Reactant) (52)

T2 P1
(ΔSr )T2 ,P2 – (ΔSr )T1 ,P1 = (ΔCP )r ln + Δng Rln (53)
T1 P2

(ΔHr )T2 – (ΔHr )T1 = (ΔCP )r (T2 – T1 ) (54)

12 Gibb’s Energy (G)

G = H – TS (55)
dG = q + Wnon–PV + WPV + PdV + VdP + TdS + SdT (56)
: 0  :+0 TdS +  :0
dG = q + 
Wnon–PV +WPV + PdV
 +VdP
 SdT


dG = q – TdS


dGsys = –T dSsurr + dSsys (57)

12.1 Calculation of ΔG
1. Case-I For a substance not undergoing chemical/phase change
dG = VdP – SdT (for reversible path) (58)
At constant Temperature: dG = VdP (59)
1.1 For ideal gas
 
P1
ΔG = –nRTln (60)
P2
1.2 For solids/liquids
ΔG = V (P2 – P1 ) (61)

2. Case-II For chemical/phase change

G = H – TS
ΔGr = ΔHr – TΔSr (62)

ΔHr ΔSr ΔGr Feasible/Not Feasible

-ive +ive -ive Feasible at any T (Temperature)
+ive -ive +ive Not Feasible at any T
+ive +ive -ive At High T
+ive At Low T
-ive -ive -ive At Low T
+ive At High T

ΔG = 0 =⇒ Reversible
ΔH
Teqlbm = (63)
ΔS

12.2 Relationship between ΔGo and Keq

I don’t even know how to write the explanation here... But I would like to remind you this is where the dy/dx thing happened!
(We’re all looking at you, AA, beware)
I’m not even going to try to write the explanation, so here’s the formulae:
ΔGr = ΔGor + RTlnQ (64)
ΔGor = –RTlnK (65)
ΔHo
 
K2 1 1
ln = – (66)
K1 R T1 T2

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12.3 Relationship between ΔG and non-PV work

–dG ≥ Wnon–PV,by (67)

Decrease in Gibb’s Energy is equal to the maximum amount of Non-PV work which can be obtained from a system (or can be done
by the system).

12.4 Helmhottz energy

q ≤ TdS
:0
dU – WPV – TdS ≤ W non-PV
At constant T, V
d(U – TS) ≤ 0
dA ≤ 0 (68)
A = U – TS (69)
dA = 0 Reversible
dA < 0 Irreversible
dA > 0 Impossible

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