Winter 2013 Chem 254: Introductory Thermodynamics

Chapter 2: Internal Energy (U), Work (w), Heat (q), Enthalpy (H) ................................................ 13
Heat Capacities ......................................................................................................................... 16
Calculating U, H, w, q in Ideal Gas ........................................................................................ 18
Isothermal Compression ........................................................................................................... 21
Reversible Process (limiting process) ....................................................................................... 22
Isothermal Expansion ............................................................................................................... 22

Chapter 2: Internal Energy (U), Work (w), Heat (q), Enthalpy (H)
Internal Energy (excludes motion and rotation of vessel)

Look at isolated part of universe

U U system U Environment

Total = isolated
First law of thermodynamics:
- Total U for isolated system is constant
- Energy can be exchanged between various components
- Energy forms can be interconverted
Eg. Chemical En Heat Work
Utotal U system U environement 0

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

Work
In classical mechanics, move object a distance d with force F in direction of
displacement is work N m = J

F mg

d h

w mgh (kg m s-2 m = N m = J)

w mgd cos
w mgd

cos

h
d

h
mgh
d

General formula
w F dL Line integral

PV work (constant external pressure)

m applies constant force P

F
A

F
( Ah) Pext (V1 V2 )
A
Vinitial ) Joules, or L Bar (1 L Bar = 100 J)

w mgh Fh
w Pext (V final

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

More general formula for PV work, P does not need to be constant
Vf

w Pext dV
Vi

Sign Convention : Work done on the system raises internal energy of system ( w 0 )
Work done by the system lowers the internal energy ( w 0 )
Other forms of work:
- electrical work
w Q

Q is charge in coulombs

difference in potential (in Volts or J/C)

Run a current over
Q I t
I is current (in Amps or C/s)
w It
Important:

Work is associated with a process, with change. Work is transitory. You

cannot say that a system contains that amount of energy or heat

Heat:

associated with a process going from State 1 State 2

U system q w

q is heat; w is the work

Heat is exchanged between system and environment

q 0 : system loses energy

q 0 : system gains energy
qsystem qenvironment

note: Tsystem Tenvironment for heat to flow

Isolated system

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

Touter Tinner (regulate)

So there is no flow of heat

U system U environment 0
U inner 0

Beaker + Lab + = environment (isolated)

U I 0 ; U II 0
U I U II 0

Chemical Energy

Butane + O2 CO2 H 2

Note : U II 0 even if temperature increases!

Why? Chemical energy of butane is converted to heat.

Heat Capacities
The amount of energy (heat) required to raise the temperature of 1 gram of substance
by 1 oC. Heat capacity of water is 4.18 J/g K = 1 calorie
1) Heat capacity is dependent on heat
Eg. 10 oC 11 oC and 80 oC 81 oC, require slightly different energies
2) At least 2 types of heat capacity
a) Keep volume constant CV
b) Keep pressure constant CP
3) Heat capacity is proportional to amount of substance
Molar heat capacities : CP ,m , CV ,m
n moles : CV nCV ,m , CP nCP,m

4) General formula
Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

Tf

qV CV dT
Ti

If CV is constant over temperature range:

qV CV dT CV T T f CV T f Ti
i
Ti
Tf

qV CV (T )

And

qP CP (T )

Which is larger CP or CV ?
Relation for CP and CV for ideal gas?

V2 V1 ; T2 T1

U qP w qP Pext (V2 V1 )
U qP nR(T2 T1 )

PV nRT

qP CP T ; U qV CV T

CP T CV T nRT
CP CV nR

or

CP,m CV ,m R

Therefore CP is larger than CV . At constant P , the system also does PV work when
raising T . (analysis for ideal gas)
No work because V is constant

U qV w qV
U CV T

Bomb calorimetry

qVsystem qVsurrounding CVCalorimeter Tmeasure

U reaction

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

qPsystem qVsurroundings
qPsystem CVCalorimeter Tmeasure
qPsystem H reaction

True definition of Enthalpy

H U ( PV )

PV PV
2 2 PV
1 1 ; for PV
1 1 PV
2 2;

H U PV
At constant Pressure

H U PV
2 2 PV
1 1
H U P V
H qP w P V qP P(V ) P(V )
H qP CP T

Completely general : U , H are function of state

specify T ,V , P

U U (T2 , P2 ,V2 ) U (T1 , P1 ,V1 )

H H (T2 , P2 ,V2 ) H (T1 , P1 ,V1 )

Change in U , H are the same for both paths

Change in q, w are different for different
paths

Calculating U, H, w, q in Ideal Gas

1) Calculating U , H is easy if T is known

U U (T ) U CV dT CV T ]Tif CV T f Ti
Tf

Ti

U CV T

for any process

H H (T ) .....

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

H CP T

for any process (if CP is constant)

We know CP CV nR
Special cases:
Isothermal Process T is constant T 0 ; U H 0
2) Work: w Pext dV
- Constant V

PV work only

Vi V f w 0 ;

q qV U

Vf

- Constant Pext w Pext dV Pext (V f Vi )

Vi

; q qP H

Isothermal reversible process: (Reversible process: delicate, see later)

1
nRT is constant
Pext nRT
V
V f dV
V
w nRT
nRT ln V V f
i
Vi V
Vf
nRT ln V f ln Vi nRT ln
Vi

Vf
w nRT ln
Vi
3) Heat
Adiabatic process :

q 0 by definition
U q w ; U w

Adiabatic Reversible Process

nRT
V
V f nRT
U w
dV
Vi
V
nRT
nCV ,m dT
dV
V
dT nR
nCV ,m

dV
T
V

q 0 , U w ,

Pext

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

dT
i T
Tf
nCv ,m ln
Ti
nCV ,m

dV
V

Vf
nR ln

Vi
nR

Tf
Vf
ln ln
R
Ti
Vi
For adiabatic reversible process:
Cv ,m

P
C
Tf
Vf
Tf
ln ln OR P ,m ln ln i
P
R
R
Ti
Vi
Ti
f

Cv ,m

V f CP ,m Pi
ln
OR ln
P
V
C
i
V
,
m

Tf
Vf
ln ln
R
Ti
Vi

Cv ,m

1)

Tf
Vf
V f CV , m
R
ln
ln ln
CV ,m Vi
Ti
Vi

Tf
Ti

Vf

R
CV , m

Vi

Tf
Vf
ln ln
R
Ti
Vi

Cv ,m

2)

nRT f
Tf
P
ln ln
i
P
R
nRTi
Ti
f

CV ,m

Tf
ln
Ti

Pi

Pf

P
Tf
ln ln i
P
Ti
f
P
CV ,m
Tf
1 ln ln i

P
R
Ti
f

Pi
CV ,m R T f
ln

ln

Ti
Pf

P
Tf
ln ln i
P
R
Ti
f

CP , m

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

Adiabatic Isobaric Process
Constant external pressure AND q 0

Isothermal Compression

Constant external pressure

w Pf V f Vi 0

q w 0 (because U 0 because isothermal)

What is work in 2-step process?

w2 Pint Vint Vi Pf V f Vint

w2 w1 ; q2 q1

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

Conclusion: w and q depend on details of process, not only on initial and final state.
Repeat for 3 step, 4.

w5 w4 w3 w2 w1 ; q5 q4 q3 q2 q1

The more steps, the less w and less heat

Reversible Process (limiting process)

Pext Pgas at each step
nRT
V
Isothermal Reversible Process
Pext

dV
Vi
Vi V
Vf
V
nRT ln |Vif nRT ln
Vi
Vf

w Pext dV nRT

Vf

work, q is minimal

Isothermal Expansion

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

w1 Pf V f Vi 0 ;

q1 w1 0

w2 w1 ; q2 q1

w3 w2 w1 ; q3 q2 q1

More processes more work ( w ), more heat ( q )

w5 w4 w3 w2 w1 ; q5 q4 q3 q2 q1
Limiting Expansion Work
ansion
wlcompression
wlexp
imit
imit

Vf

Vf

Vi

Vi

wlimit Pext dV nRT

Vf
dV
nRT ln
V
Vi

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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Winter 2013 Chem 254: Introductory Thermodynamics

Grains of sand : I can run process either way
The thermodynamic work is the same both ways for reversible process
Irreversible Process (Big chunks of mass)

Follows arrows in reverse: add mass, piston rises? ; removes mass, piston lowers?
This is absurd, hence:
Why do irreversible processes run in one way and not another?
What is special about irreversible?

Chapter 2: Internal Energy, Work, Heat and Enthalpy

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