First Law of Thermodynamics

CHAPTER 2
First Law of Thermodynamics
FIRST LAW OF THERMODYNAMICS

Thermodynamics is based on laws that have never been observed to be violated
Two types of quantities 1) State functions: Depend only on the thermodynamic state of the system not on how the system got there (e.g., P, T, V, ...)

Two types of quantities 1) State functions: Depend only on the thermodynamic state of the system not on how the system got there (e.g., P, T, V, ...) 2) Process-dependent quantities: Depend on the way in which the system changes its thermodynamic state
Pa, Ta, Va system state a surroundings

system Pa, Ta, Va system state a surroundings state b Pb, Tb, Vb

system Pa, Ta, Va system state a surroundings state b Pb, Tb, Vb

Two types of processes 1) Reversible: System and surroundings are infinitesimally close to equilibrium throughout the process. 2) Irreversible: System and/or surroundings not in equilibrium except at beginning and at the end (sometimes in between).
Natural processes: irreversible
P-V WORK
Work (mechanical): Involves moving an object against a force (e.g., gravity, friction, piston)
w1 w2
Work (w) depends on the specific path system state a
system state b
w3
surroundings
Work may be Positive: work done on the system Negative: work done by the system
P-V WORK
Force = gravity F n d r A
System
= Pext A F n d w = F r
A = area
| n| = 1
d w = F r = Pext A n r = Pext Adr w = Pext dV
Expansion: dr > 0 Compression: dr < 0
dV > 0 dV < 0
w < 0 w > 0
P-V WORK
Force = gravity F n d r A
System
w = Pext dV
w1
system
w2
Vf
state b
w=
Pext (T, V )dV
system state a
Vi
w3
surroundings
Line integral
P-V WORK
Examples
n = 1 mole of gas
T1 = T2 = T P1, V1, T P2, V2, T
Pext P1 P2
w=
Vf
Pext (T, V )dV
Vi
w = P2 (V2 V1 ) w<0
V1 V2 V work is done by the system
P-V WORK
Examples
n = 1 mole of gas
T1 = T2 = T P1, V1, T P2, V2, T
Pext P1 P2
w=
Vf
Pext (T, V )dV
Vi
w = P1 (V2 V1 ) w<0
V1 V2 V work is done by the system
P-V WORK
Examples
n = 1 mole of gas
T1 = T2 = T P1, V1, T P2, V2, T
Pext P1 Pa P2
w=
Vf
Pext (T, V )dV
Vi
w = Pa (Va V1 ) P2 (V2 Va ) w<0

V1 Va V2 V work is done by the system
P-V WORK
Examples
n = 1 mole of gas
T1 = T2 = T P1, V1, T P2, V2, T
Pext P1 P2
w=
Vf
Pext (T, V )dV
Vi
V1
V2
P-V WORK
Examples
n = 1 mole of gas
T1 = T2 = T P1, V1, T P2, V2, T
Pext P1 P2
w=
Reversible process
The system is always infinitesimally close to equilibrium
Vf
Pext (T, V )dV
Vi
P = Pext
V1 V2 V
P-V WORK
Pext P1 P2
Examples
n = 1 mole of gas T1 = T2 = T
V1
V2
w=
Vf
Pext (T, V )dV P = Pext V2 w = RT ln V1
Vi
Reversible process
The system is always infinitesimally close to equilibrium:
Ideal gas
RT P = V
w = RT
V2
V1
dV V
Maximum amount of work that can be done by (on) a system at constant T
HEAT
Heat is the entity that flows across a boundary between two systems or between a system and its surroundings as a result of a temperature difference between them
Molecular scale: kinetics energy transferred via motion and/or collisions and/or radiation
Convention: Heat flows from higher T to lower T
A process that involves no heat flow is adiabatic Observation When an infinitesimal amount of heat flows at constant pressure into a system the temperature of the system increases according to
q = CP dT CP (T ) :
Heat capacity at constant pressure (depends on the system)
HEAT
q = CP dT qP = CP =
T2
CP (T )dT
T1
Heat capacity at constant pressure:
q T
Convention:
qP > 0
heat flows into the system
Heat may be transferred reversibly or irreversibly
IMPORTANT
(1) A system doesnt have a q or w. They arent state functions (2) q and w may both lead to a temperature change (3) q and w have same units

It is based on experimental observations and can be stated in various ways
qcycle + wcycle = 0
b
In general q and w are different from zero and depend on the specific path
( q + w) = 0
( q + w) +
path a
path b
( q + w) = 0
( q + w) +
1 path a
2 path b
( q + w) = 0
1 path a
( q + w) =
1 path b
( q + w)
q + w =
exact differential !!!
dU = q + w
U = internal energy (extensive state function)
INTERNAL ENERGY
Properties
dU = 0
The internal energy of a system that undergoes a cyclic process does not change
U =
1 independent of the path
dU = U2 U1
The change in internal energy of a system whose state change from 1 to 2 depends only on the initial and final state and is independent of the way in which the change occurs
INTERNAL ENERGY
Important
(1) Knowing U means knowing the function not just one value U(n,T,V) or U(n,T,P) for single component systems U(n,T,P,x1,x2,...,xN-1) for multicomponent systems
(2) Thermodynamics doesnt really care about the absolute value of U but only about the difference U between two states the zero can be set anywhere (be consistent!!!)
HEAT CAPACITY AT CONSTANT V

dU = q + w
dU = q Pext dV
Constant volume process:
dV = 0
dU = q
Heat capacity at constant V
Cv =
U (n, V, T ) T
V,n
Heat absorbed with an infinitesimal change in temperature in a constant volume process Change in internal energy with an infinitesimal change in temperature in a constant volume process
HEAT CAPACITY AT CONSTANT V

U (n, V, T ) T
V,n
Cv =
Heat absorbed with an infinitesimal change in temperature in a constant volume process Change in internal energy with an infinitesimal change in temperature in a constant volume process
Molar capacity: Divide by the number of moles
Um
U = n Um (V, T ) T
CV,m (T ) =
RELATIONS INVOLVING U
Changes in U(V,T) associated with a change in the thermodynamic state (single component, homogeneous system for now) Recall:
z = z (x, y ) z x 1
dz =
z x
dx +
y
z y
dy
x
z x
= x x y
z y
y z
= 1
U = U (V, T ) dU = U T dT +
V
U V
dV
T
CV = U V U V
U T
dU = CV dT +
V
U V
dV
T
V T
T U
= 1
U T
T V
U = U (V, T ) dU = U T dT +
V
U V
dV
T
CV =
U T
dU = CV dT +
V
U V
dV
T
U V
U T
T V
U V
= CV
T V
U V
= CV J
J = Joule coefficient J = 0
for ideal gas
U T U V
dU =
dT +
V
dV
T
dU = CV dT CV J dV
U(V,T) convenient because: (1) dU can be related to measurable quantities (CV, J) (2) dU = dq when dV = 0, no work (T,P can change but there is no compression or expansion)
ENTHALPY
Many experiments involve constant P
Enthalpy:
H = U + PV dH = dU + P dV + V dP = q + w + P dV + V dP = q Pext dV + P dV + V dP = q + (P Pext )dV + V dP
ENTHALPY
dH = q + (P Pext )dV + V dP
At constant pressure:
P = Pext
dH = q
Heat capacity at constant P
Cp =
H T
CV =
p
U T
CP > CV

CP includes heat adsorbed to cause temperature rise and system expansion CV does not involve system expansion
ENTHALPY
dH = H T dT +
P
H P
dP
T
dH = CP dT +
Following the same procedure as for U(T,V)
H P
dP
T
Joule-Thomson coefficient
dH = CP dT CP
T P
dP
H
JT =
JT = 0
T P
H for ideal gas
dH = CP dT CP JT dP
SUMMARY
Changes associated with the equation of state as well as with the first law of thermodynamics that can be expressed in terms of measurable quantities Expansion coefficient
1 (T, P ) = V
V T
Isothermal compressibility
P,n
1 (T, P ) = V
V P
T,n
Heat capacity at constant P
CV =
U T
=
V
q dT
Cp =
V
H T
=
p
q dT
Joule coefficient
J =
T V
1 = CV
U V
Joule-Thomson coefficient
JT =
T P
1 = CP
H P
SUMMARY
Relation between heat capacities Heat capacity at constant V Heat capacity at constant P
CV =
U T
=
V
q dT
Cp =
V
CP CV = CP CV = CP CV =
H T
H T
U T
=
p
q dT
(U + P V ) T +P
P
U T
U T
V T
U T
SUMMARY
Relation between heat capacities
CP CV =
But,
U T
+P
P
V T
U T
dU =
U T
dT +
V
U V
dV
T
At constant P,
dUP =
U T
dTP +
V
U V
dVP
T
dividing by dTP
U T
=
P
U T
+
V
U V
V T
SUMMARY
Relation between heat capacities
CP CV =
Using
U T +
+P
P
V T V T
U dT
U T
=
P
U T
U V
CP CV =
U V
+P
T
V T
SUMMARY
dU = CV dT CV J dV
dH = CP dT CP JT dP
JOULE EXPERIMENT
dU = CV dT + U V dV
T
J =
dU = CV dT CV J dV
adiabatic walls
T V
1 = CV
U V
adiabatic walls
vacuum plug T1, V1 T2, V2
adiabatic walls vacuum
q=0 w=0
U = 0
Pext = 0
T V
JOULE-THOMSON EXPERIMENT
dH = CP dT + H P dP
T
dH = CP dT CP
adiabatic walls
T P
JT = dP
T P
P1 > P2
porous plug
P1
adiabatic walls
P2 P1, V1, T1
dH = CP dT + H P dP
T
dH = CP dT CP
adiabatic walls
T P
JT = dP
T P
P1 > P2 P2
P1
adiabatic walls
dH = CP dT + H P dP
T
dH = CP dT CP
adiabatic walls
T P
JT = dP
T P
P1 > P2 P2
P1
adiabatic walls adiabatic walls reversible process
P2, V2, T2
q=0
w = P dV
w = P1 (0 V1 ) P2 (V2 0)
first law
q=0 w = P1 V 1 P2 V 2
U2 U1 = P1 V1 P2 V2
U1 + P1 V1 = U2 + P2 V2
H 1 = H2
constant enthalpy!!!
dH = CP dT + H P dP
T
dH = CP dT CP
adiabatic walls
T P
JT = dP
T P
P1 > P2 P2
P1
adiabatic walls
P2, V2, T2
H = 0 T P
JT = T P 1 = CP H P
Low T / High P:
H P H P
>0
T
JT < 0
High T / Low P:
<0
T
JT > 0
JT = T P 1 = CP H P
Low T / High P:
H P H P
ISENTHALPIC CURVES
>0
T
High T / Low P:
<0
T
It is possible to use the J-T experiment to liquefy gas (see book)
PERFECT GAS
P V = nRT U V =0
T
U = U (T ) dU = CV dT CV = CV (T ) H = U + P V = U + nRT H = H (T ) dH CP = CP (T ) = dT
PERFECT GAS
P V = nRT U V =0
T
CP CV =
U V
+P
T
V T
V T
nR = P
CP CV = nR

First Law of Thermodynamics

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CHAPTER 2

First Law of Thermodynamics

FIRST LAW OF THERMODYNAMICS

FIRST LAW OF THERMODYNAMICS

Pa, Ta, Va system state a surroundings

FIRST LAW OF THERMODYNAMICS

system Pa, Ta, Va system state a surroundings state b Pb, Tb, Vb

FIRST LAW OF THERMODYNAMICS

system Pa, Ta, Va system state a surroundings state b Pb, Tb, Vb

FIRST LAW OF THERMODYNAMICS

Natural processes: irreversible

d w = F r = Pext A n r = Pext Adr w = Pext dV

Expansion: dr > 0 Compression: dr < 0

Pext (T, V )dV

T1 = T2 = T P1, V1, T P2, V2, T

Pext (T, V )dV

T1 = T2 = T P1, V1, T P2, V2, T

Pext (T, V )dV

T1 = T2 = T P1, V1, T P2, V2, T

Pext (T, V )dV

w = Pa (Va V1 ) P2 (V2 Va ) w<0

T1 = T2 = T P1, V1, T P2, V2, T

Pext (T, V )dV

T1 = T2 = T P1, V1, T P2, V2, T

Pext (T, V )dV

Pext (T, V )dV P = Pext V2 w = RT ln V1

Maximum amount of work that can be done by (on) a system at constant T

Convention: Heat flows from higher T to lower T

Heat capacity at constant pressure:

heat flows into the system

Heat may be transferred reversibly or irreversibly

FIRST LAW OF THERMODYNAMICS

FIRST LAW OF THERMODYNAMICS

exact differential !!!

1 independent of the path

HEAT CAPACITY AT CONSTANT V

Heat capacity at constant V

HEAT CAPACITY AT CONSTANT V

Molar capacity: Divide by the number of moles

H = U + PV dH = dU + P dV + V dP = q + w + P dV + V dP = q Pext dV + P dV + V dP = q + (P Pext )dV + V dP

Heat capacity at constant P

Heat capacity at constant V

H for ideal gas

Heat capacity at constant V

Heat capacity at constant P

vacuum plug T1, V1 T2, V2

adiabatic walls vacuum

It is possible to use the J-T experiment to liquefy gas (see book)

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