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Chapter 2-1erprin

Chapter 2 discusses the first law of thermodynamics, emphasizing the relationship between internal energy, heat, and work in closed systems. It covers various transformations, including isochoric, isobaric, isothermal, and adiabatic processes, detailing how energy is conserved and how heat capacities are defined. The chapter also introduces mathematical relationships, such as the Mayer relation, and explores the behavior of ideal gases under different conditions.

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19 views18 pages

Chapter 2-1erprin

Chapter 2 discusses the first law of thermodynamics, emphasizing the relationship between internal energy, heat, and work in closed systems. It covers various transformations, including isochoric, isobaric, isothermal, and adiabatic processes, detailing how energy is conserved and how heat capacities are defined. The chapter also introduces mathematical relationships, such as the Mayer relation, and explores the behavior of ideal gases under different conditions.

Uploaded by

wahab.ayoub1234
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chapter 2

First law of thermodynamics


1-First principle-Internal energy:
During an elementary transformation; a closed
system exchanges work δW and a quantity of heat
δQ with the outside.
The internal energy U of this system then
undergoes a variation:
dU= δW+ δQ
The first principle postulates that the variation
in internal energy ∆U during a transformation
of a closed system is equal to the algebraic sum
of the quantities of heat and work exchanged
between the system and the external
environment.

∆U =Q+W

U is a state function; it does not depend on the


path followed.
A- In a cyclical transformation:
The initial state coincides with the final state (UA=UB);
we therefore have ∆U=0; ∆Ucycle=(W+Q)cycle=0
This relationship reflects the principle of equivalence
between work and heat during a cycle: W = -Q
B- In an isolated system:
The system does not exchange energy with the external
environment; W=0 et Q=0 ∆U=0
The first principle is a principle of conservation of
energy.
2-Isochoric transformation; isobaric-enthalpy:
The first principle; applied to closed systems which passes
from a state (1) to a state (2); is written as follows:
∆U=U2 - U1=Q + W
2 2
W = ʃ-PedV ∆U = Q- ʃ PedV
1 1
a- Isochoric transformation:
V=Cte dV=0 W=ʃ- PedV=0 ∆U = Qv
The index “v” reminds us that this variable is constant
during the transformation
The variation in internal energy during an isochoric
transformation is equal to the quantity of heat
exchanged with the exterior.
b- During an isobaric transformation:
Pe=P=cte W = -Pe ʃdV = -Pe(V2-V1) = -Pe∆V
∆ U = Qp- P ∆V
Qp= ∆U+P ∆V = U2-U1+P(V2-V1)
=U2-U1+PV2-PV1
Qp = ∆(U+PV) = ∆H
Qp = H2-H1= ∆H
At constant pressure; the quantity of heat exchanged
is equal to the variation of a new state function called
enthalpy (H).
Recapitulation:
dU = δW+ δQ ∆U=W+Q
dH =d(U+PV) ∆H = ∆U+ ∆(PV)

Isochoric transformation W=0 ∆U = Qv


et ∆H = Qv+V∆P
Isobaric transformation W = -P ∆V
∆U = -P ∆V + Qp et ∆H = Qp

In these particular cases heat is a state function


Qv= ∆U
Qp= ∆H
3- Calorific or thermal capacities:
Consider a system characterized by the state
variables P;V;T during a reversible transformation;
the heat exchanged is such that : δQ =dU- δW
Giving the expression of the differential δQ as a function of
independent state variables (P ,V);(P ,T)and (V ,T).
δQ δQ
δQ =( dP )vdP+( d V )p dv
δQ δQ
δQ= ( )T dP +( )p dT
dP dT
δQ δQ
δQ= ( )T dV + ( )v dT
dV dT
Special cases:
a- In an isobaric transformation:
dP=0 δQp= CpdT Cp= ( δQ
d T)p

Cp: Heat capacity at constant pressure

b- In an isochoric transformation:
δQ
dV= 0 δQv= CvdT Cv = ( d T )v

Cv : Heat capacity at constant volume.

c- In an adiabatic transformation:
δQ = 0
4- Mathematical aspect of the first principle:
Joule established two laws which an ideal gas obeys
Joule's 1st law:
Internal energy is only a function of temperature
U=U(T)
∂u ∂u
So : =0; = 0 ; dU= CvdT
∂P ∂V
Joule's 2nd law:
Enthalpy only depends on temperature
H=H(T) ∂H ∂H
So : =0 =0
∂P ∂V
dH=CpdT
-Relationship between Cp and Cv:
Let the relation giving H: H= U+PV
Like PV=nRT; in the case of an ideal gas; we have H=U+nRT
Let's derive this equation with respect to the temperature(n=cte)
dH/dT = d(U+nRT)/dT = dU/dT+nRdT/dT
Cp = Cv + nR………..(1)
Cp-Cv = nR ; this is the Mayer relation
By asking : γ = Cp/Cv; the Mayer relation is written :
Cv((Cp/Cv)-1) = nR Cv(γ-1) = nR
Cv = nR/γ-1 in (1): CP = (nR/γ-1)+nR = nRγ/γ-1
Remarks:
1/ The molar heat capacities are:
Cv=R / γ-1 et Cp=Rγ / γ-1
2/ If cp and cv are the specific heats of a gas:
Then the heat capacities of this gas of mass m are:
Cp = mcp et Cv = mcv
3/Like specific and molar heats; heat capacities vary with
temperature.
Cp=Cp(T) et Cv= Cv(T) ∆H =ʃ Cp(T)dT
and ∆U=ʃ Cv(T) dT
5-Isothermal transformation:
T=cte ; dT=0;
-In this case; dH = Cp.dT=0; dU = Cv.dT= 0
dU=δW+ δQ=0 δW = -δQ W=-Q et δW =-PedV
-Irreversible case: W = -Pe∆V = -Q
-Reversible case: W = -nRTln(V2 / V1 ) = -Q
Remarks:
PV=cte P1V1=P2V2 V2 / V1= P1/ P2
W=-nRTln(V2 / V1)= nRTln(P1 / P2)
6- Adiabatic transformation :
Consider a closed adiabatic system (δQ=0)
dU= δW + δQ = δW
- irreversible case: dU = δW = -PedV=CvdT
-reversible case: dU= δW = -PdV=CvdT= -nRTdV / V
We therefore have the equation :CvdT= -nRTdV / V
dT /T= -nRdV
Cv V
We have already seen that: Cv = nR / γ-1
nR / Cv = γ-1
From where : dT / T = -(γ-1)dV / V
If the system evolves from stat1 (T1;V1) to stat2
T2 V2
(T2;V2);we will have:ʃ dT = -(γ-1)ʃ dV (we suppose
T1 T V1 V
γ=cte) ln(T2/T1)=(γ-1)ln(V1/V2)=ln(V1/V2) (γ-1)
lnT2/T1=ln(V1/V2) (γ-1)
T2V2 γ-1 =T1V1γ-1 = cte
TVγ-1 = cte
By combining this equation with that of ideal gases
PV=nRT; we can establish the existing relationships
between the variables (Pet V) and (P and T) during an
adiabatic transformation.
Between P and V:
T=PV / nR
TVγ-1 = (PV/ nR) Vγ-1 =(P / nR)Vγ PVγ = cte
Between P and T:
V = nRT/P
T(nRT/P) γ-1 =(nR) γ-1 .T γ.P 1-γ = cte
T γ P 1-γ = cte or T.P (1-γ/ γ)

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