Chapter 2 First principle of thermodynamics

2.1. Concept of work:

2.1.1. Expression of the work of the pressure forces:
Work is defined as the action of an external force on an object over a distance. It is equal to
the product of the force (F) times the displacement (x).

δW= - Fe dx = - Pe Sdx = -Pe dV (S : Surface)

After integration, we find: W = -∫ (Pe : external pressure)
For a reversible transformation, we have: Pe=P (P: system pressure)
As a result, W = -∫

Units of work :
[W] = Pa.m3 = Joules
[W] = l. atm 1 l.atm = 101.325 J
[W] = Cal 1 Cal = 4.185 J

Note:
W = -∫
 If V2<V1 (compression), ΔV<0 and W>0, indicating that the system receives work
from the external surroundings.
 If V2>V1 (expansion), ΔV>0 and W<0, indicating that the system provides work to the
external surroundings.

2.1.2. Work for the different transformations for an ideal gas:

Reversible case:
a) Isochoric Transformation (V constant , dV =0) :
Wrev = 0
b) Isobaric Transformation:
Wrev = -Pext (V2-V1) = -P (V2-V1) = -nR (T2 – T1 )
c) Isothermal Transformation:
W = -∫ = -nRT∫ = -nRTln = nRTln = nRTln = P1V1ln

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(P1V1 = P2V2)

Irreversible Case
a) Isochoric Transformation (V constant, dV =0) :
Wirr = 0
b) Isobaric Transformation:
Wirr = -Pext(V2-V1) = -P2(V2-V1)
c) Isothermal Transformation:
Wirr = -Pext (V2-V1) = -P2 (V2 - V1) = -P2 ( - ) = nRT( - 1)

2.2. Concept of Heat Q :

2.2.1. Définition :
Heat ( Q ) is a form of energy that is transferred from one part of a system to another
or to another system by virtue of a difference in temperature.
In this case, the amount of heat exchanged is proportional to the temperature difference. (∆T
= T2-T1) and to the mass (m) of the system.
The expression for the quantity of heat (or heat) is:

δQ =m. c’ . dT
Q=∫

m: mass of the substance (g or Kg).

c’: Specific heat capacity (cal (J) / g(Kg).°C(K)).
∆T: temperature variation (°C or K).
T1: initial temperature (K).
T2: final temperature (K).
m : masse du corps (système) s’exprime en g ou en Kg
Units of heat :
[Q] = Joule (J)
[Q] = calorie (cal)

Note:
We can also write:
∫
If c’ is constant, we will have:

With:
n: number of moles.
c: Molar specific heat capacity (cal (J) / mol.°C(K)).
Note:
Q<0 the reaction is exothermic.
Q>0 the reaction is endothermic
Q=0 the reaction is athermic
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2.2.2. Specific heat capacity (c):

Specific heat, also called specific heat capacity is the quantity of heat required to raise the
temperature of one unit mass (1g) or one mole (1mol) of a substance by one degree celsius (1
°C) (or one kelvin (1 K)).
We distinguish the following different types of specific heat capacity:
• Specific heat capacity “c’v” (molar “cv”) at constant volume.
• Specific heat capacity “c’p” (molar “cp”) at constant pressure.
Example
c water, liquid = 1 cal/g °C = 18 cal/mol °C

2.2.3. Heat capacity (C):

Is the product of the specific heat capacity (molar) of a substance by its mass (number of
moles). It is expressed in cal (J) / K.
C = m.c’= n.c
c’ = =
So: Q = C.∆T
There are two types of heat capacity:
Cv: heat capacity at constant volume.
Cp: heat capacity at constant pressure.
For Cp, Cv, cp and cv; we have the following two cases:

Case of pure bodies in the solid or liquid states: cp ≈ cv, and, Cp ≈ Cv

Case of pure bodies in the gaseous state: cp ≠ cv, and, Cp ≠ Cv

2.2.4. Heat capacity for ideal gases:

 Monoatomic ideal gases:
Examples : He, Ar, Ne...

With:
n: number of moles.
R: ideal gas constant.
 Diatomic ideal gases:
Examples : O2, N2, H2...

 Relationship between cp and cv for an ideal gas:

cp and cv are linked by the Mayer relation: cp – cv = R
We also have : (γ: adiabatic constant)
From these two relationships; we find:

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cp (cal/mol.K) cv (cal/mol.K) γ=
Monoatomic gas: 5 3 1,66
Ar, Ne, He
Diatomic gas : H2, N2, O2 7 5 1,40
Other gases: H2O, CO2 8 6 1,33

2.2.5. Quantities of heat for the different transformations:

*Isochoric transformation:
∫ ∫ ∫
( ) ( )
*Isobaric transformation:
∫ ∫ ∫
( ) ( )
*Isothermal transformation:
(According to the first law of thermodynamics)
( ) ( )
*Adiabatic transformation:

2.2.6. Latent heat

Latent heat of a substance is the amount of energy absorbed or released by the substance
during a change in its physical state that occurs without changing its temperature.

Or: The latent heat, denoted L, is the amount of heat required to transform one unit of mass
(or one mole) of a pure substance from one physical state to another at p=1atm.

Q = m. Ľ
Where,
L is Latent Heat in J.kg-1 ou cal.kg-1
Q is Amount of Heat Released or Absorbed
m is Mass of substance
Or Q=nL
Where: n is the number of moles and L is the latent heat expressed in J.mol-1 or en cal.mol-1.
Latent heat is called by various names depending upon the phase it changes.
 Solid-to-Liquid: Latent Heat of Fusion Lf>0
Liquid to solid: Latent Heat of Solidification Ls = -Lf <0
 Liquid-to-Gas: Latent Heat of Vaporization Lv >0
 Solid-to-Gas: Latent Heat of Sublimation Lsub>0

Exemple :
 The latent heat of fusion of water at 0°C under P = 1atm, Lf = 80.4 cal / g
 The latent heat of vaporization of water at 100°C under P = 1atm, Lv = 535 cal / g

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Calculating Heat Required for Phase Change

For a pure substance with mass m in a solid state at temperature T1, receiving heat quantity Q
leads it to a gaseous state at temperature T2. The heat quantity necessary for this mass to
transition from T1 to T2 is:

Q = Q1 + Q2 + Q3 + Q4 + Q5
Q=∫ ∫ + mLv + ∫
Q = mcp solid (Tf – T1) + mLf + mcp liquid (Tv – Tf) + mLv + mcp gaz (T2 – Tv)

2.3. Internal energy:

2.3.1. Définition :
Internal energy, U is the total energy of a system. It includes the kinetic energy, potential
energy, chemical energy, Electrostatic energy etc. of the system. Thermodynamics is not
concerned about calculating the internal energy of a system. However, it is more important to
observe the change in internal energy (ΔU) of a system.
The change in internal energy during a transformation from an initial state to a final state is:

∆U = W + Q

2.3.2. First principle of thermodynamics

The first principle of thermodynamics, also known as the law of conservation of energy, states
that the total energy of an isolated system remains constant. This means that energy cannot be
created or destroyed, but it can be converted from one form to another. The principle is based
on the concept of energy conservation.

2.3.3. Other statement of the first principle:

a) Conservation principle:
For an isolated system, we have: Q = W = 0, therefore: ∆U = U2 - U1 = Q + W = 0
Thus, U1 = U2
The internal energy of an isolated system remains constant.

b) Equivalence principle:

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Consider a closed system undergoing a cyclic transformation. The initial state and the final
state coincide. There fore: U1 = U2

c) Initial and final state principle:

Consider a set of transformations that take a system from an initial equilibrium state 1 to a
final equilibrium state 2.

State 1 State 2

∆U = U2-U1 = WA + QA = WB + QB
But WA ≠ WB et QA ≠QB
∆U depends only on the initial and final states and not on the path taken. This principle
implies that the internal energy U is a state function.

Note:
Q and W are not state functions.

2.3.4. Differential expression of internal energy:

For an elemental transformation, we have: dU = δQ +δW

2.3.5. Consequences of the first principle:

a) At constant volume:
∆U = U2 – U1 = Qv + W = Qv - ∫
Isochoric transformation V = constant dV = 0 W=0
∆U = U2 – U1 = Qv
∆U represents the heat exchanged at constant volume.

b) At constant pressure:
∆U = U2 – U1 = Qp + W = Qp – p (V2 – V1)
U2 – U1 = PV1 – PV2 + Qp Qp = (U2 + PV2) – (U1 + PV1)
We define a new state function H = U + PV H : Enthalpy of the system.
Qp = H2 – H1 = ∆H
∆H <0 the reaction is exothermic.
∆H >0 the reaction is endothermic.

The heat of reaction at constant pressure is equal to the change in enthalpy of the
system, and therefore it only depends on the initial and final states.

Relationship between heat of reaction at constant volume and heat of reaction at

constant pressure:

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Chapter 2 First principle of thermodynamics

Qp = H2 – H1 = (U2 + PV2) – (U1 + PV1) = U2 – U1 + PV2 – PV1

Qp = Qv + n2RT – n1RT QP = Qv + ∆nRT

2.3.6. Applications of the first principle

1. Joule's laws:
Joule's first law:
The internal energy is only a function of temperature.
U = U (T) ; dU = CVdT ; CV =( )V
ΔU = Qv = ∫ =∫
If cv is constant ΔU = ncvΔT

Joule's second law:

Enthalpy is only a function of temperature
H = H(T); dH = CpdT ; Cp =( )p
ΔH = Qp = ∫ =∫
If cp is constant ΔH = ncpΔT

Relationship between ΔU et ΔH :
ΔH = ncpΔT = =γ ΔH = γ ΔU
ΔU = ncvΔT

2.3.7. Specific transformations:

1. Isothermal transformation:
State 1 T1 = T2 = T State 2
n, P1, V1, T n, P2, V2, T

P1V1 = nRT P2V2 = nRT

P1V1 = P2V2

 ΔU = ncvΔT = 0
 ΔH = ncpΔT = 0
ΔU = Q + W = 0 Q = -W
 W = -nRTln = nRTln = nRTln = P1V1ln

 Q = nRTln = nRTln

Isochoric transformation :
State 1 V =V =V State 2
1 2

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n, P1, T1, V n, P2, T2, V

P1V = nRT1 P2V = nRT2

 W=0
 ΔU = Q + W = Qv = ncvΔT
 ΔH = γ ΔU = ncpΔT

Isobaric transformation:
State 1 P1 = P 2 = P State 2
n, V1, T1, P n, V2, T2, P

PV1 = nRT1 PV2 = nRT2

 W =-P (V2 –V1)

 ΔU = Q + W = ncvΔT
 Qp = ΔH = ncpΔT

Adiabatic transformation:
State 1 Q=0 State 2
n, P1, T1, V1 n, P2, T2, V2

P1V1 = nRT1 P2V2 = nRT2

dU = δQ + δW
δQ = 0, donc dU = δW
Pour un gaz parfait nous avons:
dU = ncV dT = n (R /γ-1) dT
δW = - PdV = (-nRT / V) dV
As a result
n (R/ γ -1) dT = (-nRT/V) dV dT/T = -(γ -1) (dV/V )
ln (T) = -( γ - 1) ln (V) + cst
ln (T) + ln (V ) γ - 1 = ln (TVγ – 1) = cst
TVγ – 1 = cst
Therefore, : T1V1γ -1 = T2V2γ -1

TV γ -1 = k PVγ = K’ P1V1γ = P2V2γ

T = PV / nR

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TV γ -1 = k TγP 1-γ= K’’ T1γP11-γ = T2γP21-γ

V = nRT/ P

T1V1γ -1 = T2V2γ -1
P1V1γ = P2V2γ Laplace's law
γ 1-γ γ 1-γ
T1 P1 = T2 P2
Work done by pressure forces during a reversible adiabatic transformation of an ideal
gas.:

ΔU = Q + W = ncvΔT = ncv(T2-T1) = ncv = (P2V2 – P1V1)

On a cp-cv = R, γ =
W= (P2V2 – P1V1) =

W=
Exercice d’application :
1mol of NO (supposedly perfect gas) is subjected to the following successive transformations:
• An isothermal reversible compression from an initial state to state 2.
• An adiabatic reversible expansion from state 2 to state 3.
• An isobaric heating that brings it back to the initial state.

1) Calculate V1, V2, T2, T3 if P1=2atm=P3. P2=10 atm and T1=300K.

2) Calculate for each transformation (in joules) the following quantities: Q, W, ∆U, ∆H.
Given: Cv= 3/2R ; Cp=5/2R
Solution :
1) Calculation of parameters
P1V1 = nRT1 V1 = nRT1/P1 V1 = 12,3 L
 V2 will be obtained using the relation:
P1V1 = P2V2 V2 = V1 (P1/P2) V2 = 2,46 L
T1=T2=300K (isothermal transformation)
• To determine V3, we apply the relation
P2V2γ= P3V3γ V3= V2 (P2/P3)1/γ V3 = 6,46 L
 The temperature T3 is obtained by applying the relation for ideal gases;
P3V3= n RT3 T3= P3 V3 /nR T3=157,6 K

2) Calcul des différentes grandeurs :

Isothermal transformation 1→2
∆U12= 0 , ∆H12= 0 (since there is no temperature variation)
∆U12 =0= Q12 +W12 Q12 = - W12 W12 = -nRTln W = 4014,26J
Q12 = - 4014,26J
Adiabatic transformation 2→3
Q 23 = 0 => W 23= ∆U23=n cv (T 3 –T2) = - 1776 J
∆H = ncp (T 3 –T2) = -2960 J

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IsobaricTransformation 3→1
W31 = -P∆V= -P (V1-V3)=2 (12,3 - 6,46)= - 11,68 L .atm = - 1184J
∆U31 = - ncv (T1 –T3)=1 .3/2. 8,31 (300- 157,6)= 1776 J
Q23=∆ H 23= ncP (T1 –T3)=1. 5/2. 8,31 (300- 157,6) = 2960 J

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