CHEM 2011

CH2: HEAT & WORK

CHEM 2011
CH2: HEAT & WORK

2.1 The Internal Energy and the First Law of Thermodynamics

2.2 Heat
2.3 Work
2.4 Equilibrium, Change, and Reversibility
2.5 The Work of Reversible Compression or Expansion of Ideal Gas
2.6 The Work of Irreversible Compression or Expansion of Ideal Gas
2.7 Other Examples of Work
2.8 State Functions and Path Functions
2.9 Comparing Work for Reversible and Irreversible Processes
2.11 Heat Capacity
2.12 Determining ∆U and Introducing the Sate Function Enthalpy
2.13 Calculating q, w, ∆U and ∆U for Processes Involving Ideal Gases
2.14 Reversible Adiabatic Expansion and Compression of an Ideal Gas
CHEM 2011
CH2: HEAT & WORK

CHAPTER 2
End of Chapter questions for practice:
Q: 2, 4, 6, 7, 17, 18, 19, 25, 28
P: 6, 7, 8, 10, 11, 16, 19, 23, 26 (Tf = 315K),
29, 30, 32 (process is at constant P),
37, 38, 41a, 44b (final answer correct, but missing value of n in the equation),
48, 52 (The solution in the manual is correct for the question written in the text book. The
question in the solution manual has a typo - Cv,m = 5/2R should be Cv,m = 3/2R),
53 (units in answer should be “J” not “J/mol”)

Corrections to the solutions given in the solutions manual are shown in blue.
CHEM 2011
CH2: HEAT & WORK

is sometimes defined as the study

of the relation of temperature to
the macroscopic properties of the
system.
THREE LAWS OF THERMODYNAMICS

FIRST LAW: energy is conserved.

SECOND LAW: the entropy of an isolated system always increases.

THIRD LAW: the entropy of any pure perfect crystal can be

chosen as equal to zero at 0 K.
CHEM 2011
CH2: HEAT & WORK
5% work (light)

ENERGY: The capacity to

supply heat or do work. 95% heat
100% electricity
UNITS
1 Joule = 1 kgm2/s2 (small)
1 calorie = 4.184 J
1 dietary “Calorie” = 1000 calories When energy is transferred from one object
to another, it appears as work and heat.

Energy = work + heat

CHEM 2011
CH2: HEAT & WORK

Energy cannot be created or destroyed;

it can only be converted from one form
to another., or transferred from one
object to another.
• Energy is the capacity to do work.
• In thermodynamics we are interested
in the flow of energy, particularly in
the forms of heat and work.
• Heat and work describe the process Kinetic Energy (EK): The energy of motion.
Etotal = EK + EP Potential Energy (EP): Stored energy.
of energy transfer.
CHEM 2011
CH2: HEAT & WORK KINETIC ENERGY

Q How can a material store energy? In gases molecules are in In solids molecules
rapid random motion vibrate like springs
On the molecular scale, we think in terms of:
MOLECULAR VIBRATION MOLECULAR ROTATION
THERMAL ENERGY = kinetic energy of
molecular motion (translational, rotational,
and vibrational)
measured by finding the temperature. POLARIZABLE MOLECULES IN AN ELECTRIC FIELD

CHEMICAL BOND ENERGY = potential

energy stored in molecular bonds
CHEM 2011
CH2: HEAT & WORK

Energy cannot be created or

destroyed: it can be converted
form one form to another
Or
The total energy of the Universe
is constant

Euniv = E sys + E surr = 0

E sys = −E surr E = E final − Einitial
CHEM 2011
CH2: HEAT & WORK

THE TOTAL ENERGY OF THE SYSTEM: Esys = KE + PE + U

▪ KE is kinetic energy
▪ PE is potential energy
Energy cannot be created or
destroyed: it can be converted
▪ U is internal energy; consists of translational, vibrational,
form one form to another electronic, nuclear energies, and energy of intermolecular
Or interactions
The total energy of the Universe
is constant
For the system at rest and with no external fields:

E sys = U
Euniv = E sys + E surr = 0
E sys = −E surr ΔUtotal = ΔUsystem + ΔUsurroundings
CHEM 2011 DIFFERENT PROCESSES
CH2: HEAT & WORK

is a state function (path Isothermal = constant T process ΔTsys = 0

independent), so we are only Isobaric = constant P process ΔPsys = 0
interested in the final (U2) and Isochoric = constant V process ΔV = 0
initial (U1) states. Adiabatic = no heat transferred q= 0

U = U2 − U1 P
P2, V2, T2 P1, V1, T1

Δ refers to change that occurs as a result of an arbitrary

process. In simplest processes, only one of P, V, or T changes

FIRST LAW OF THERMODYNAMICS

V

U = q + w Cyclic = implies that final state=initial

state (no change in any property state
HEAT WORK of system)
CHEM 2011 INPUT H2(g) + ½ O2(g) → H2O(l)
CH2: HEAT & WORK

OUTPUT q q+w w
In all 3 systems, the reaction between hydrogen and oxygen occurs, but the output
resulting from the change in internal energy is different

U = q + w

ΔrU = Uproducts - Ureactants

CHEM 2011 WORK in thermodynamics is defined as a quantity of energy that
CH2: HEAT & WORK “flows” across the boundary between the system and surroundings
that can be used to change the height of a mass in the surroundings.

P1, V1, T P2, V2, T

WORK in classical mechanics Compression

work is being
is the product of a force times done on the gas.
distance
h1
Work = -Force × distance h2
= - mass × acceleration × distance The walls are
adiabatic.
= - m × g × (h2 – h1)
= -mgΔh

m is in units of kg; w is in Joules; WORK: is not a state function….it depends on the path taken.
h is in meters; g = 9.8 m/s2 E.g. irreversible expansion versus reversible expansion
CHEM 2011
CH2: HEAT & WORK

w= -mgΔh

SIGN OF WORK CONVENTION

-
+ +
Work done on the system;
Energy of the system increases
e.g. compression ΔV <0
+
Work done by the system;
- -
Energy of the system decreases
+ e.g. expansion ΔV >0
CHEM 2011 U = q + w
CH2: HEAT & WORK Q• How does the gas change molecularly to
increase the internal energy of the gas? U = 0 + w The walls are adiabatic
Q• How does the temperature change? w0
U  0

P1, V1, T1 The walls are adiabatic P2, V2, T2

Compression work is
being done on the gas.

h1
h2
CHEM 2011
CH2: HEAT & WORK

Which of the following changes increase the internal energy of a gas in a

sealed container with adiabatic walls?

a. Increasing the volume of the container

b. Decreasing the temperature of the container

c. Decreasing the volume in the container

d. Releasing 10% of the gas molecules from the container

CHEM 2011
CH2: HEAT & WORK Fex
Pex P > Pex expansion Work = -Force × distance

P < Pex compression Infinitesimal amount of work

Δh > 0 w<0
dw = -Fexdh
Δh P V
System Negative sign: we move the
Δh < 0 w>0 object against an opposing force

Pex is the external force per unit area: Pex = Fex /A

V2

The volume change:

Then:
dV = A dh
dw = -Fexdh = -(Fex /A) × A dh = -Pex dV

w = − Pex dV
V1
CHEM 2011 Consider a chemical reaction that occurs in a cylinder fitted with a
CH2: HEAT & WORK EXAMPLE piston that results in a net production of gases

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g)

6 mol of gas 7 mol of gas Δn = 1

In an adiabatic system
(no heat exchange)
How can energy be transferred
to surroundings?
… in the form of WORK…..

w = - P × ΔV
w = - ΔnRT
• As gas is produced the container expands….lifts weight
Δn = νproduct gases - νreactant gases
• Energy is transferred to surroundings as work
CHEM 2011
CH2: HEAT & WORK

A greatly simplified model of an internal combustion engine is as follows. At the

start of the power stroke the ignited gases exert a pressure of 20 atm, and drive the
piston back against a constant force equivalent to 5.0 atm. In so doing, the piston
sweeps out 250 cm3. What is the power output of a six-cylinder engine working at
2000 RPM (with one power stroke from each cylinder every second revolution)?

ANSWER
1 L atm = 101.325 J Work per one stroke w = - (5.0 atm) × (0.250 L) = - 1.25 L atm
w = - 1.25 L atm (101.325 J/(Latm)) = - 1.3 × 102 J
1
Six such cylinders produce 2000  6   w = 7.8  105 J in one minute
2

Rate of production is: (7.8  105 J)/(60s) = 13kW

CHEM 2011
a) How much work has been done if 5 g of Zn have completely reacted according
CH2: HEAT & WORK Q to the following reaction if the external pressure is 1 atm and T=298K.
b) What’s the work per 1 mole of Zn consumed?

Zn(s) + 2H+(aq) + 2Cl-(aq) H2(g) + Zn2+(aq) + 2Cl-(aq)

5g
n(H2 ) = n(Zn) = = 0.0765mol
65.38g / mol
n(H2 )RT 0.0765mol(0.08206Latm / mol − K )(298K )
V = = = 1.87L
P 1atm

Work is done against the external pressure of 1 atm!

 J 
A w = −PV = −(1atm)(1.87L) 101  = −189 J
 Latm 
Work is done by the system when 5 g of Zn react

B
CHEM 2011
CH2: HEAT & WORK

EXAMPLE: SURFACE EXPANSION

We will be dealing with expansion work!

CHEM 2011
CH2: HEAT & WORK
COMPRESSION / EXPANSION
work =  F  dl = −  PexternaldV

ELECTRICAL WORK
Welectrical done by the surroundings on the system:

welectrical = Q = It = ( current ,voltage ,time )

WP-V done by the system on the surroundings:

wP −V = −  PexternaldV

Total work = It −  PexternaldV = It − Pexternal (Vf − Vi )

CHEM 2011
CH2: HEAT & WORK
To find ΔU= U2-U1 we pick a convenient path to get from the initial
state 1 to the final state 2 and find w and q along this path.

P P
U1 U1

is a state function (path

U2 U2
independent), so we are only
interested in the final (U2) and
initial (U1) states.

V1 V2 V V1 V2 V

 U  U 
FOR IDEAL GASESU =fU(T=) fonly; U f(V);
( T ) only; U f(P)
U  f(V); U  f(P)   = 0 = 0
 V TV T

IMPORTANT: w and q are not state functions: they are path-dependent!

CHEM 2011
CH2: HEAT & WORK

P P P
1 A 1 B 1 C

2 2
2

V1 V2 V V1 V2 V V1 V2 V

In which case, has the greatest amount of work been done?

A) A Diagram
B) B Diagram
C) C Diagram
CHEM 2011
CH2: HEAT & WORK

Heat is transitory – i.e. only appears during energy flow

is the transfer of energy HIGH TEMP LOW TEMP

between two entities that Heat is transferred from a hot entity to a cold entity if
are at different energy as heat the two are in contact through a diathermic wall
temperatures.

Heat is not a state function;

it is path dependent.
EQUAL TEMP If the two entities have identical temperatures, there is
no net transfer of energy as heat even though the two
regions are separated by a diathermic wall. This
condition corresponds to thermal equilibrium.
CHEM 2011
CH2: HEAT & WORK

Conservation of energy requires

qsystem + qsurroundings = 0
qsystem = -qsurroundings
SIGN OF HEAT CONVENTION Tsystem
+ Heat added to the system Tfinal > Tinitial
- Heat removed from system Tfinal < Tinitial
CHEM 2011
CH2: HEAT & WORK
The amount of heat transferred will depend on the path taken to increase the
temperature.

1. The system may be heated on a Bunsen burner or heated by

How much heat is transferred in
raising the temperature of a
beaker of water (50 g) from 25°C
to 35°C (at constant P = 1 atm)?
immersing the beaker in a warmed water bath.
heat = q= m × s × ΔT
= (50 g) (4.184 J/g deg) (10 deg)
= 2092 J

2. The system may be heated by sonicating or mixing on a stir

plate in which case mechanical work is used to increase
temperature and q=0

3. Or could increase T by combination of heating in water bath

and mechanical mixing then q lies between 0 and 2092 J
CHEM 2011
CH2: HEAT & WORK
The previous example illustrates that

A) work
B) heat
C) internal energy

is a state function
CHEM 2011
CH2: HEAT & WORK
HEAT: For a closed system with no phase changes and no chemical reactions.

T2 T2


q = C dT = mC dT
T1

T1

▪ C = heat capacity of the system

Heat capacity is
amount of heat ▪ C = specific heat capacity [c] = J/g K or J/mol K
needed to change ▪ m= mass of the system
temperature of a
substance by a given If C = const. in the temperature range between T2 and T1
amount

q = mC (T2 − T1 )
CHEM 2011
CH2: HEAT & WORK

q
HEAT CAPACITY (C) C= measured in J/K
T

MOLAR HEAT CAPACITY (Cmoles ) C q

Heat required to raise the temperature C= = measured in J/(mol K)
of 1.00 mole of substance by 1.00°C. n nT

SPECIFIC HEAT CAPACITY (Cs) q

Heat required to raise the temperature Css =
Cmass
C measured in J/(g K)
of 1.00 g of substance by 1.00°C. mT
CHEM 2011
CH2: HEAT & WORK

q = mCs (T2 – T1)

…when heat is added to a substance its temperature will rise…

How much the temperature will rise depends on:

1. the amount of heat delivered
2. the amount of substance present
3. the chemical nature and physical state of the substance
4. conditions under which heat is added to substance
CHEM 2011
CH2: HEAT & WORK

Which one of these quantities is extensive, and

which one intensive: C, Cs, Cmoles?

A) C is intensive, Cs is extensive and Cmoles is intensive

B) C is intensive, Cs is extensive and Cmoles is extensive

C) C is extensive, Cs is intensive and Cmoles is intensive

D) C is extensive, Cs is extensive and Cmoles is intensive

CHEM 2011
CH2: HEAT & WORK

U qV
AT CONSTANT VOLUME CV = =
T T

At constant V the heat absorbed by the system is equal to the change in internal energy

• Heat capacity is a quantity
that can be measured
directly
• can be measured at
constant volume or
constant pressure
H qP
AT CONSTANT PRESSURE CP = =
T T
At constant P the heat absorbed is equal to the change in enthalpy
It follows that:
U = CV T = nC V T Assuming CV and CP are
independent of
temperature….only true
H = CP T = nC P T at T < 300 K
CHEM 2011
CH2: HEAT & WORK CONSTANT PRESSURE CONSTANT VOLUME
q is used to increase ΔU and for expansion work q is only used to increase ΔU

In general CV and CP for a

substance are not
dTP < dTV
equal…WHY? …because in CP > CV
a constant pressure
process, volume is
changing (expansion!) so
work must be done on
the surroundings….

Q How are Cp and Cv related for a gas? Cp – Cv = nR or Cp,m – Cv,m = R

…this is true mainly only for gases, because the volume of liquids and solids doesn’t change much with
temperature, so work done on the surroundings is very small…. CP  CV for liquids and solids
CHEM 2011
CH2: HEAT & WORK U
REMEMBER… calculating heat capacity for gases heat capacity C =
T
U = Etranslation + Erotation + Evibration + Eelectronic

Heat capacity of liquids > gases and can’t be accounted for just by considering
translational, rotational, and vibrational contributions…..

Q ……there are weak interactions present between molecules in the liquid and
solid state, which contribute to the increase in C
How does the heat
capacity (C) of a gas
differ from that of a EXAMPLE: CP H2O(l) > CP H2O(g)
Energy must be absorbed into
liquid?
the system to break up weak
hydrogen bonding interactions
present between water
molecules in the liquid state.
CHEM 2011
CH2: HEAT & WORK

q
C = lim
T →0 T − T
f i

Q Heat capacity is which kind of variable?

a) intensive b) extensive
CHEM 2011
CH2: HEAT & WORK
The total change in internal energy from initial to final state:
a) Depends on the intermediate state

b) Does not depends on the intermediate state

State function depends on state of system not path to reach that state

final

U =  dU = U f − Ui
initial
dU is an exact differential

 dU = U f − Ui = 0
a cyclic path
 T1 < T2 < T3
CHEM 2011
CH2: HEAT & WORK

1. work 2. heat

For the
compression

Pex would depend on the mass - therefore w would always differ

V2

w = −  Pex dV = −Pex (V2 − V1 ) = −Pex V U = U(T3 ,V2 ) − U(T1 ,V1 ) = q + w

V1

We can choose a different path from V1, T1 to V2, T3 and a different path from V2, T3 to V1, T1
Since w is different for each path, the cyclic integral of work ≠ 0
Since ΔU is the same and w always differs, then q will be different as well.
Both q and w are path functions.
CHEM 2011
CH2: HEAT & WORK Q Does U depend on T and V? ΔU = qv + w = CvdT +PdV (in general)
Internal energy of an ideal gas is a function of T:
True False

Internal energy of an ideal gas is a function of V:

True False

Volume change increases or decreases U by changing T

 U 
FOR IDEAL GASES U = f ( T ) only; U  f(V); U  f(P)   =0
 V T

For isothermal process

(when ΔT = 0) U = 0 and qT = −wT
CHEM 2011 If the rate of change of the macroscopic variables is negligibly small, the system
CH2: HEAT & WORK passes through a succession of states of internal equilibrium as it goes form the
initial to the final states.

All combinations of P, V, and T consistent with PATH

1 mol of an ideal gas lie on the coloured surface. (Pi , Vi, Ti) (Pf , Vf, Tf)

CLASSES OF QUASI-STATIC PROCESSES

1. REVERSIBLE
If an infinitesimal opposing change
in the variable that drives the
process causes reversal in the
direction of the process.

2. IRREVERSIBLE
If an infinitesimal change in the
driving variable does not change
the direction of the process.
CHEM 2011
CH2: HEAT & WORK

INTERNAL EQUILIBRIUM = systems are homogeneous

▪ Change conditions ▪ If rate of process is too fast,

from i to f molecules can’t keep up to
keep system homogeneous.
▪ Change very slowly so
always maintain
equilibrium ▪ For this course assume quasi-
static processes so can assign
single value of P, V, T and n for
system and surroundings
CHEM 2011
CH2: HEAT & WORK

Q What happens if we add a very small

weight to side A?

REVERSIBLE – an infinitesimal change in the

driving variable does change the direction of
the process

B IRREVERSIBLE – an infinitesimal change in

the driving variable does not change the
A direction of the process
CHEM 2011
CH2: HEAT & WORK

QUASI-STATIC PROCESS FROM i TO f

REVERSIBLE
rate of movement along line is:
(a) slow (b) fast

IRREVERSIBLE
rate of movement along line is:
(a) slow (b) fast
CHEM 2011
CH2: HEAT & WORK
P
• PV diagrams are used when the pressure
1 and volume are known at each step of
P1 the process
• The state of the gas at each step can be
plotted on a graph called a PV diagram

2 This allows us to visualize the process

P2 through which the gas is progressing

• The curve is called the path

V1 V2 V
CHEM 2011 ISOTHERMS: plot of pressure versus volume of gas at the
CH2: HEAT & WORK same temperature. On a PV-diagram it is a hyperbola.

for an isothermal
process, T is constant,
nRT is a constant
isotherms
So that,

A – isochoric (const. V)
C – isothermal (const. T)
D – isobaric (const. P)
B – adiabatic (no heat transfer)
CHEM 2011
CH2: HEAT & WORK

If a gas is undergoing an isobaric expansion, what happens

to the temperature?

A) increases

B) decreases

C) stays the same

CHEM 2011
CH2: HEAT & WORK
1. Have a gas expanding against a vacuum
meaning no weight (remove mass from piston)

Pex = 0

Pex = 0 so − Pex V = 0 thus w=0

CHEM 2011
2. Have a gas expanding against a mass
CH2: HEAT & WORK
so gas expands against a constant external pressure

If Pex = constant ≠ 0
As gas expands Pin decreases
For gas to expand Pin > Pex

initial state final state

w = −Pex (V2 − V1 ) = −Pex V IRREVERSIBLE PATH

For example if Pex = 3 atm and Pin = 10 atm….the gas will only expand
until Pin = 3 atm….then expansion will stop!
CHEM 2011
CH2: HEAT & WORK
3.00 moles of an ideal gas at 27.0°C expand isothermally from an initial volume
of 20.0 L to a final volume of 60.0 L. Calculate w for this process
(a) for expansion against a constant external pressure of 1.00 atm.

GIVEN V1 = 20.0 L V2 = 60.0 L P = 1.0 atm

w for an expansion against a constant pressure is:

w = −pext  (V2 − V1 ) = −(1.00 atm)  (60L − 20L) = − 40 L atm

we can convert this into JOULES….using

the conversion factor 1Latm= 101.325 J

w = −40 L atm  ( 101.325 J/ 1 L atm) = −4053 J = −4.1  103 J

CHEM 2011
CH2: HEAT & WORK Is it possible to have the system perform a greater amount of work for
Q
the same increase in volume?
A Yes.

Example: Suppose that the weight on the piston is made up of an

infinitesimal number of small weights each of which contribute to a total
external pressure of 10 atm….

Pin = Pex (i.e. Pin = 10 atm, Pex = 10 atm)

Removing one weight will decrease Pex by infinitesimal amount so Pin > Pex
and gas will expand by infinitesimal amount until Pin = Pex

We can continue to do this by progressively removing one weight at a

time….gas expands by infinitesimal amount with removal of each weight…
CHEM 2011
CH2: HEAT & WORK IRREVERSIBLE PATH
Initial : Pin = 10 atm
Pex = 10 atm Gas expands until
after weight lifted Pex = 1 atm
Pin = 1 atm
Final : Pin = 1 atm
Pex = 1 atm

Same final state, but the

REVERSIBLE PATH work done by the two
systems is very different!!!
Mass consists of infinite
number of small weights
that are removed one at a Weights removed until
time… Pin = 1 atm
Final : Pin = 1 atm
Pex = 1 atm
Initial : Pin = 10 atm
Pex = 10 atm
Pex = gets reduced gradually from 10 atm to 1 atm
CHEM 2011
CH2: HEAT & WORK

In a reversible path the system remains infinitely close to equilibrium!

Note: Integration is needed when Pex changes during the process.

REVERSIBLE PATH P − Pex = dP ; T = const.

V2


w = − Pex dV
V1
V2


w = − (P − dP)dV
V1 V2


V2
Since
V2 w = − (nRT / V )dV

w = − PdV
V1
P = nRT / V w = −nRT ln
V1 V1
CHEM 2011
CH2: HEAT & WORK WORK done is equal to the area under P versus V curve

IRREVERSIBLE PATH w = −Pex V Real processes are always irreversible.

(2) EXPANSION
w = −P2(V2 − V1 )
(1) Work is given by the total area in red

COMPRESSION
w = −P1(V1 − V2 )
Work is given by the total area in red and yellow

wtotal = −P2(V2 − V1 ) − P1(V1 − V2 ) = −(P2 − P1 )(V2 − V1 )  0

CHEM 2011
CH2: HEAT & WORK WORK done is equal to the area under P versus V curve

REVERSIBLE PATH
A truly reversible process can never really be done. Reversible
processes allow us to estimate the maximum amount of work that
could be done!

V2
w = −nRT ln
V1

Note that for reversible processes, the areas under

the P-V curves are the same in the forward and
reverse directions

V2 V1
wtotal = −nRT ln − nRT ln = 0
V1 V2
CHEM 2011
CH2: HEAT & WORK
EXPANSION
System doing work on surroundings
|wreversible| ≥ |wirreversible|

Get maximum work from system

when process reversible

COMPRESSION
Surroundings doing work on system
|wreversible| ≤ |wirreversible|

Have to put more work into system

to drive process when process is
irreversible
CHEM 2011
CH2: HEAT & WORK

The difference between the expansion and compression processes results from the requirement that Pext < P
at the beginning of each expansion step, whereas Pext > P at the beginning of each compression step.

IRREVERSIBLE PATH REVERSIBLE PATH

w = −Pex V V2
w = −nRT ln
For an isothermal expansion V1

wirrev  wrev

For an isothermal compression

wirrev  wrev
CHEM 2011
CH2: HEAT & WORK

Which of the following diagrams illustrates the work done in

a five step irreversible expansion?

A B

A) A
C D
How would you actually
B) B Q
calculate that work?
C) C

D) D
CHEM 2011
CH2: HEAT & WORK
3.00 moles of an ideal gas at 27.0°C expand isothermally from an initial volume
of 20.0 L to a final volume of 60.0 L. Calculate w for this process
(b) for a reversible expansion

GIVEN V1 = 20.0 L V2 = 60.0 L P = 1.0 atm

V2
w = −n R Tln
V1
(60L)
( )
w = −(3.00 mol)  8.314472 J K −1 mol−1  (300 K )  ln
(20L )
= - 8.22  103 J

Where initial and final pressures are given instead of volumes, you can express V 1 and V2
in terms of pressures

V2
w = −n R Tln
nR T nR T V1
V1 = and V2 =
P1 P2 P
w = −n R T ln 1
P2
CHEM 2011
CH2: HEAT & WORK
U = U2 − U1 = q + w
For a closed system with no phase changes and no chemical reactions
T2 T2

HEAT applied or removed from the system: 

T1

q = C dT = mc dT
T1

If C =const. in the temperature range between T2 and T1 q = mC (T2 − T1 )

V2
WORK done on or by the system

w = − Pex dV
V1

When Pex = const w = −Pex (V2 − V1 )

U = U2 − U1 = q + w = mC ( T2 − T1 ) − Pex (V2 − V1 )
CHEM 2011
CH2: HEAT & WORK
▪ Compression: work done on or by the system at Pex = constant
U2 − U1 = mC ( T2 − T1 ) − Pex (V2 − V1 )

▪ No volume change: V2 – V1 = 0;

w = 0; U2 − U1 = q = Cv ( T2 − T1 )

▪ No heat change at Pex = constant

q = 0; U2 − U1 = w = −Pex (V2 − V1 )

▪ No temperature change: U2 – U1 = 0;

P2 V1
w = −q = nRT1 ln = nRT1 ln
P1 V2
CHEM 2011
CH2: HEAT & WORK
1. Work is a form of energy transfer……another form is heat

2. In an isothermal expansion, maximum amount of work is done by a

reversible process (when compared to an irreversible process)

3. Expansion only occurs when there is a pressure difference

i.e. when Pexternal < Pinternal
when Pexternal = Pinternal expansion stops

4. The amount of work done depends on how the process is carried out….this
means work is not a state function…work is path dependent!

A change in any state function depends only on the initial and

final states not on the path taken to get from initial to final.
CHEM 2011
CH2: HEAT & WORK

1 mol H2O(l) Irreversible 1 mol H2O(g)

T = 298 K T = 298 K
P = 1 atm P = 1 atm

Temperature Reversible, Temperature Reversible,

increase Constant P decrease Constant P

1 mol H2O(l) Reversible 1 mol H2O(g)

evaporation
T = 373 K T = 373 K
P = 1 atm Constant T, P P = 1 atm

FIND energy change through reversible paths!

CHEM 2011
CH2: HEAT & WORK
▪ In general, for a change from State 1 to State 2
H = U + (PV ) = U + PV + VP + PV

▪ P = const. (isobaric process); P = Pext; Pext= const.

is defined as: H = U + PV = U − w = qp

▪ ΔH is also a function of T only for an ideal gas.

H = U + PV
H = CP ( T2 − T1 )
U, P, V are all state functions,
hence, H is a state function.
For an infinitesimal change in temperature: dH = dU + d(nRT ) = dU + nRdT
Substituting dH=CPdT and dU=CVdT into the equation: C P dT = C v dT + nRdT
C P = C v + nR
C P − C v = nR
CP −Cv = R
CHEM 2011
Consider the following reaction at constant pressure….
CH2: HEAT & WORK
2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g) ΔH = -367.5 kJ

U = H − PV
Volume of H2 generated at 1 atm is 24.5 L So –PΔV = -24.5 Latm = -2.5 kJ

Δ Δ ΔU = -370.0 kJ

So there is a small difference between ΔU and ΔH

▪ ΔH slightly less negative than ΔU since system did expansion work when H2
was generated (….so some of the internal energy released is to do work)
▪ In general the difference between ΔU and ΔH for rxns. involving gases is
ΔPV = RTΔn (at constant T)
▪ However, in reaction only involving the condensed states (i.e. liquids and
solids) the changes in volume are so minimal….that
ΔU  ΔH (also in reactions involving gases when Δn = 0)
CHEM 2011
CH2: HEAT & WORK
Calculate ΔH and ΔU for the transformation of 1.00 mol of an ideal gas from 27.0°C
and 1.00 atm to 327°C and 17.0 atm if

T
C P,m = 20.9 + 0.042 in units of J K −1 mol−1
HEAT K

CAPACITY For an ideal gas, ΔH is given by:

CHEM 2011
CH2: HEAT & WORK

Calculate q, w, ΔU and ΔH for each segment and for the cycle

assuming that the heat capacity is independent of temperature.
GIVEN 𝐶𝑣,𝑚 = 20.79 J mol-1 K-1 𝑛 = 2.50 mol 𝑇 = 𝑇1 = 𝑇3

ISOTHERM
STEP 1: (1.00 L, 16.6 bar) to (25 L, 16.6 bar) At Constant Pressure
𝑃2 𝑉2 𝑃1 𝑉1 𝑛𝐶𝑣,𝑚
∆𝑈1→2 = 𝑛𝐶𝑣,𝑚 (𝑇2 − 𝑇1 ) = 𝑛𝐶𝑣,𝑚 − = (𝑃2 𝑉2 − 𝑃1 𝑉1)
𝑛𝑅 𝑛𝑅 𝑛𝑅

(20.79𝐽𝑚𝑜𝑙 −1 𝐾 −1 )
∆𝑈1→2 = 𝑞 + 𝑤 𝑞 = ∆𝑈1→2 − 𝑤 ∆𝑈1→2 = (16.6 𝑏𝑎𝑟 × 25.0 𝐿 − 16.6 𝑏𝑎𝑟 × 1.0 𝐿)
0.08314 𝐿 𝑏𝑎𝑟 𝑚𝑜𝑙 −1 𝐾−1

𝑞1→2 = 99.6 𝑘𝐽 −(-39.8) kJ

∆𝑈1→2 = 99.6 𝑘𝐽
𝑞1→2 = 139.4 𝑘𝐽
𝑤1→2 = −𝑃𝑒𝑥𝑡𝑒𝑟𝑛𝑎𝑙 (𝑉2 − 𝑉1 ) = - (16.6 bar)(24.0 L) × ( 100 J bar-1L-1) × (1 kJ/1000J)
At Constant Pressure
∆𝐻1→2 = 𝑞 = 139.4 𝑘𝐽 𝑤1→2 =- 39.8 kJ
CHEM 2011
CH2: HEAT & WORK

Calculate q, w, ΔU and ΔH for each segment and for the cycle

assuming that the heat capacity is independent of temperature.
GIVEN 𝐶𝑣,𝑚 = 20.79 J mol-1 K-1 𝑛 = 2.50 mol 𝑇 = 𝑇1 = 𝑇3

ISOTHERM
STEP 2: (25 L, 16.6 bar) to (25 L, P3) Constant Volume

𝑤2→3 = 0

∆𝑈2→3 = 𝑛𝐶𝑣,𝑚 (𝑇3 − 𝑇2 )

T1 = T3
∆𝐻2→3 = 𝑛𝐶𝑝,𝑚 (𝑇3 − 𝑇2 ) = − ∆𝐻1→2 ∆𝑈2→3 = 𝑛𝐶𝑣,𝑚 (𝑇1 − 𝑇2 ) = − ∆𝑈1→2

∆𝐻2→3 = −139.4 𝑘𝐽 ∆𝑈2→3 = − 99.6 𝑘𝐽 At Constant Volume 𝑞 = ∆𝑈2→3 = − 99.6 𝑘𝐽

CHEM 2011
CH2: HEAT & WORK

Calculate q, w, ΔU and ΔH for each segment and for the cycle

assuming that the heat capacity is independent of temperature.
GIVEN 𝐶𝑣,𝑚 = 20.79 J mol-1 K-1 𝑛 = 2.50 mol 𝑇 = 𝑇1 = 𝑇3

ISOTHERM
STEP 3: (25 L, P3) to (1.00 L, 16.6 bar) Constant Temperature

∆𝑈3→1 = 0
At Constant Temperature
∆𝐻3→1 = 0
CYCLE
𝑉3 1𝐿
State function 𝑤3→1 = −𝑛𝑅𝑇 = − 2.50 𝑚𝑜𝑙 8.314𝐽 𝑚𝑜𝑙 −1 𝐾 −1 79.9 𝐾 𝑙𝑛
∆𝑈 = 0 𝑉1 25 𝐿
∆𝐻 = 0 State function
𝑤3→1 = 5.35 𝑘𝐽
𝑤 = −34.5 𝑘𝐽
𝑞3→1 = −𝑤3→1 = −5.35 𝑘𝐽
𝑞 = 34.5 𝑘𝐽
CHEM 2011
CH2: HEAT & WORK

Assume the cylinder is thermally isolated , so

there is no heat exchange during the expansion:
Therefore T drops in the expansion
q=0

dU = dq + dw = dw = −PextdV

If the process is reversible we

adiabatic expansion
can replace Pext with Pint

P2 , V2, T2
P1 , V1, T1 nRT
dw = −PintdV = −PdV = − dV
V
CHEM 2011
nRT
CH2: HEAT & WORK dU = dw = −PdV = − dV
V
or

dU dV
= −R
nT V
since

dU = C VdT
divide both sides with nT

dU C VdT dT dV
= = CV = −R
nT nT T V
Integration between the initial and final states gives:

 
T2 V2
dT dV T2 V1
CV = −R C V ln = Rln
T1 T V1 V T1 V2
CHEM 2011
CH2: HEAT & WORK

T2 V1
C V ln = Rln
T1 V2

Since CP − C V = R for an ideal gas then: C V ln T2 = (CP − C V )ln V1

T1 V2
Divide both sides by CV to obtain:

(  −1)
T2 CP V1  V1   V1 
ln = ( − 1)ln = ( − 1)ln  = ln 
T1 C V V2  V2   V2 

Where:  CP 
 =
 CV 
CHEM 2011
CH2: HEAT & WORK
MONATOMICgases:
For monatomic GASES

3 5
CV = R C P = CV + R = R
2 2

 CP  5
Therefore:  =   = = 1.6666...
 CV  3

DIATOMICgas
For diatomic GASmolecules
MOLECULES( (excluding vibrations):

5 7
CV  R C P = CV + R 
2 2

 CP  7
Therefore:  =    = 1.40
 CV  5
CHEM 2011
(  −1)
CH2: HEAT & WORK T2  V1 
ln = ln 
T1  V2 

Take the exponential of both sides of the equation:

(  −1)
T2 P2V2  V1  P1V1 P2V2
= =   since =
T1 P1V1  V2  T1 T2

 V1  P2
Therefore:   =
 V2  P1
or

P1V1 = P2V2 Equation relating P and V for a

reversible, adiabatic process

NOTE: It differs from Boyle’s law (P1V1)= (P2V2) in the exponent γ, because T≠const. in an adiabatic expansion.
CHEM 2011
CH2: HEAT & WORK Alternatively, divide both sides by nR (multiply by T/PV)

 T   T 
P1V1  1  = P2V2  2 
 P1V1   P2V2 

T1V1(γ −1 ) = T2 V2(γ −1 )
Equation relating T and V for a
reversible, adiabatic process

Alternatively, divide both sides by (nR)γ (multiply by (T/PV) γ)

 
 T1    T2 
P V 
1 1

 = P2V2  
 P1V1   P2V2 
(1−  ) (1−  )
P1 T1 = P2 T2
Raise both sides of the equation to the (1/γ)th power:
[(1−  ) /  ] [( 1−  ) /  ]
= T2 P2
Equation relating T and P for a
T1 P1 reversible, adiabatic process
CHEM 2011 dT
 
U2 T2

CH2: HEAT & WORK w = dU = U2 − U1 = U = CV dT

U1 T1 T
= CV (T2 − T1 )
= nC V (T2 − T1 ) If CV = constant over ΔT range

Since: T2 < T1 then w = negative

The system changed from: State 1: P1, V1, T1 State 2: P2, V2, T2

P PERFORM AS A 2 STEP PROCESS:

STEP 1: EXPAND ISOTHERMALLY
P1 , V 1 , T 1
(P1 , V1, T1) (P2’ , V2, T1) [ΔU = 0]
1 isothermal

P2 ’ , V 2 , T 1
isochoric
STEP 2: COOL GAS ISOCHORICALLY
(P2’ , V2, T1) (P2 , V2, T2) [ΔU = nCV(T2-T1)]
2 P2 , V 2 , T 2

Because U is a state function, ΔU is the same whether the change of a gas from P1 , V1,
T1 to P2 , V2, T2 occurs directly or indirectly.
V
CHEM 2011
CH2: HEAT & WORK adiabatic expansion and compression
P

P1 , V1 When gas is compressed, T:

a) Increases b) decreases
isothermal
adiabatic

Compress Expand When gas expands, T:

P2 , V2’ P2 , V2 a) Increases b) decreases

Pressure versus volume plots of an adiabatic, reversible and an isothermal,

reversible expansion of an ideal gas. Note that the curve is steeper for an
adiabatic expansion because γ > 1
CHEM 2011
CH2: HEAT & WORK
Four compression curves are illustrated:
Adiabatic (monoatomic, diatomic, polyatomic) and Isothermal.
Which one is the diatomic one?

A) green

B) blue

C) red

D) yellow
CHEM 2011
CH2: HEAT & WORK 3.50 moles of an ideal gas are expanded from 450. K and an initial pressure of 5.00 bar to a
final pressure of 1.00 bar, and CP,m = 5/2R. Calculate w for the following two cases:
a. The expansion is isothermal and reversible.
b. The expansion is adiabatic and reversible.

V2
w for an isothermal, reversible process is then given by: w = −nRT1 ln
V1
Calculate the initial and final volume:

n R T (3.50 mol)  (8.314472 JK −1 mol−1 ) (450 K )

V1 = = = 0.0262 m3
p1 (5.00  10 Pa)
5

n R T (3.50 mol)  (8.314472 JK −1 mol−1 ) (450 K )

V2 = = = 0.1310 m3
p2 (1.00  10 Pa)
5

 V2   (0.1310 m3 ) 
w = −n R T ln  = −(3.50 mol)  (8.314472 J K mol ) (450 K )  ln
−1 −1

 1
V  (0.0262 m3
) 
w = -21076 J = -21.1 kJ
P2
Same result can be obtained by using: w = nRT1 ln
P1
CHEM 2011
CH2: HEAT & WORK 3.50 moles of an ideal gas are expanded from 450. K and an initial pressure of 5.00 bar to a
final pressure of 1.00 bar, and CP,m = 5/2R. Calculate w for the following two cases:
a. The expansion is isothermal and reversible.
b. The expansion is adiabatic and reversible.
w for an adiabatic, reversible process is then given by: w = U = CV (T2 - T1 )
5 3
CV = C P - R = R - R = R
2 2
[(1−  ) /  ] [( 1−  ) /  ]
T1 P1 = T2 P2
[( 1−  ) /  ] 5 5
[( 1− ) / ]
T1 P1  P1 
[( 1−  ) /  ]
 5 3 3
T2 = [(1− ) /  ] = T1   = 450  = 236K
P2  P2  1

 3
w = CV (T2 - T1 ) =  (8.314
J
)(3.5mol)(236K - 450K) = -9.34kJ
2 Kmol
Less work is done on the surroundings in part b) because in the adiabatic expansion, the temperature
falls and therefore the final volume is less that that in part a).
CHEM 2011
CH2: HEAT & WORK
Where: P2 = Pext and q = 0

U = w

nC V ( T2 − T1 ) = −P2 (V2 − V1 )

nRT1 nRT2
But V1 = and V2 =
P1 P2
(P1 , V1, T1) (P2 , V2, T2) nRT2 nRT1
Therefore nC V ( T2 − T1 ) = −P2 ( − )
P2 P1

If we know initial conditions and P2 we can solve for T2

CHEM 2011
An automobile tire contains air at 320  103 Pa at 20.0°C. The stem valve is
CH2: HEAT & WORK
removed and the air is allowed to expand adiabatically against the constant
external pressure of 100  103 Pa until P = Pexternal. For air, CV,m = 5/2R. Calculate
the final temperature. Assume ideal gas behavior.

Since q = 0, we have ΔU = w

n CV,m (T2 − T1 ) = − pext (V2 − V1 )

 n R T2 n R T1 
n C V,m (T2 − T1 ) = −pext  − 
 2p p1 

The factors n cancel out. Rearranging the equation gives:

 Rp   Rp  T2 = 0.804 T1 = 235 K
 CV,m + ext  T2 =  CV,m + ext  T1
 p2   p1 


 CV,m +
R pext  
( -1
) (
  2.5  8.314472 J K mol +
-1
(
3.20  10 Pa
5
)(
8.314472 J K -1 mol -1  105 Pa 
)
)

T2  p1   
= =
T1 
 CV,m +
R pext  
( ) (
  2.5  8.314472 J K mol +
-1 -1
( 5
)
)(
8.314472 J K -1 mol -1  105 Pa )

 p2   10 Pa 
CHEM 2011
CH2: HEAT & WORK