Chapter 2

The First Law

Dr. Mohamad Toutounji
Department of Chemistry

Thermodynamics is the study of the

transformation of energy; energy change
that accompanies a process

Principles of Heat Flow

Systems and Surroundings
System: part of the universe we are interested in.
Surroundings: region outside the system where
observations are made.
The system and the surrounding are separated by
boundaries

Universe: System + Surrounding

Types of System: Boundary

dependent
Open system: Matter and heat can
transfer through the boundary

Closed System: Only heat can travel

through the boundary
Isolated: Neither matter nor heat can be
transferred through the boundary

Open System

Energy

System

Matter

Surrounding

Closed System

Energy

Matter
System

Surrounding

Isolated System

En Mt

System

Surrounding

Work, heat, and energy:

Work is done when an object is moved against an opposing
force.
Energy of a system is its capacity to do work. When work is
done on a system, the capacity of the system to do work is
increased, so the energy of the system is increased.
When the system does work, the energy of the system is
reduced.

Directionandsignofheatflow(q)
qis+theheatflowsintothesystem
Heating50.0gofwateronahotplate

qistheheatflowsintothesurrounding
Cooling50.0gofwaterfrom80Cto50C
IN
ENDOTHERMIC
q(sys)>0

OUT
System

EXOTHERMIC
q (sys) <0

Differencebetweenheatandenergy
Work:isthetransferofenergythatchanges
themotionofatomsinthesurroundingsina

uniformmanner

Heat:isthetransferofenergythatchanges
themotionofatomsinthesurroundingsina

chaoticmanner

Work: Changes the height of

.weight in the surrounding
Example 1:
Electrochemical reaction:
Production of electricity to move a
motor

Example 2:
Piston

Examples of heat flow

Example 1:
H2O (s)

H2O (l) q>0

Endothermic
Example 2:
CH4(g) + 2O2 (g)
q<0

Exothermic

CO2(g) + 2H2O(l)

First Law of Thermodynamics

Relating U to Heat and Work

Energy cannot be created or destroyed.

Energy of (system + surroundings) is constant.
Any energy transferred from a system must be
transferred to the surroundings (and vice versa).
From the first law of thermodynamics:
when a system undergoes a physical or chemical change, the
change in internal energy is given by the heat added to or
absorbed by the system plus the work done on or by the
system:
U = q + w
The internal energy of an isolated system is constant

U = K.E + P.E of the molecules in the system.

U is a state function in the sense that its value depends on
the current state of the system and is independent of
how the state has been prepared:

U2

dU

U
2
1

U1

U is measured in Joules, J = 1 kg m 2/s2.

Work

Expansion work
Expansion against constant pressure
Reversible process
Isothermal reversible expansion

F = pex A
dw = -Fdz = -pex A dz
= pex dV
Free Expansion, pex = 0

Work
Expansion work
Vf

Vi

pex dV .

If the external p ex is constant

Vf

pex dV p V ; V V V
Vi
ex
f
i
Reversible expansion: pex is infinitesimally different than pgas;
pex pgas.
The process is at equilibrium, it is called reversible process.

Example: dw = -pexdV -pgasdV, pgas = nRT/V

nRT
w
dV nRT
V1
V
V2
nRT ln
V1
V2

V2

V1

dV
V

assuming isothermal process (T = 0).

On the contrary,
pex >> pgas or pex << pgas. This process is not at
equilibrium and is called irreversible process:
wirr = -pex V.

Example:
Find the work done when 50 g of iron
reacts with hydrochloric acid in (a) a
closed vessel of fixed volume (b) an open
beaker at 25 C.
(a) V = 0 , w = 0
(b) V =Vf -Vi=Vg-Vl =Vg= nRT/pex, where n
is the number of moles of H2(g) produced.
w= -pex nRT/pex= -nRT=
= -(50 g/55.85 g mol)
*(8.3145J/K.mol)*(298.15K)= -2.2kJ

Heat Capacity
The slope of U at any
T is called heat
capacity.

U
CV

T V
CV is the heat
capacity at
.Constant volume

Heat Capacity
U increases when T is raised.
As U = U(T,V), then dU dT + dV.
U
U
dU
dT

T V
V

dV
T

One can use Cv to relate U to T, dU = CvdT

U = CV T, if CV is T independent.

Enthalpy
The q supplied to the system at constant
pressure causes the change in another
thermodynamic property of the system, the
enthalpy

H U pV

Because U, p, V are all states functions, the

enthalpy is a state function.

dH dU dpV pdV
dw dq V dp pdV
pdV dq V dp pdV
dq V dp dq , at dp = 0.
dH dq H q p

dH dq dU pdV
H U pV

,For an ideal gas

H U ng RT
ng is change in amount of gas molecules in
the reaction.

Example
The value of H at 298 K and 1 bar for the reaction described
by
2H2(g) + O2(g) 2 H2O()
Is -572 kJ. Calculate U for this reaction.
Solution
The reaction is carried out at constant p = 1.0 bar, H = qp =
-572 kJ. To calculate U, V is needed (n = 3, R = 0.08314)
V = nRT/p = 74.3 L, V 74.3 L (water liquid). Using

U = H - pV
U = -572 kJ (1.0 bar) (73.4 L) (8.314/0.08206) (1/1000)
= -565 kJ.
For perfect gases,
H = U + pV = U + RTngas
using this equation will yield the same result.

Variation of enthalpy with temperature

The enthalpy of a substance increases as its
temperature increases, this increase
depends on conditions. The most
. important one is constant pressure
Slope of a plot of H versus temperature
is given by

H
Cp

Cp is heat capacity at constant pressure,

Cp/n is molar heat capacity. For infinitesimal
change in temperature

dH C p dT
H = CpT, constant pressure.
If H depends on T, Empirical expression for
Cp is

C p ,m

c
a bT 2
T

a, c and c are independent of temperature.

Example
For Nitrogen a = 28.58, b = 3.77*10 -3, c
= 0.5*10-5. It is heated from 25 C to
100 C, find the molar change in
enthalpy.

H (T2 )

H (T1 )

dH

T2

T1

c
(a bT 2 )dT 2.19kJ / mol
T

Relation between heat capacities

Cp is larger than CV
Cp-CV = nR
Cp,m - CV,m = R
The above relation is only valid for a perfect
Gas.
Cp,m - CV,m R for nonperfect gas

Enthalpy

Internal Energy
B
A

H
Cp

Temperature
Enthalpy graph ( at const P) is steeper than than the internal
Energy, therefore Cp,m > CV,m

Adiabatic Changes
A perfect gas expands adiabatically,
a difference in temperature should be expected.
As the gas expands, work is done by the
gas which cause its U to drop which will
decrease. K.E and T will go down.
U = q + w; q = 0
U = CV T
wad = CV T
CVdT = - pdV = -nRT dV/V

Reversible adiabatic
dV
CV dT pex dV nRT
V
dT
dV
CV
nR
T
V
dT
dV
CV
nR
T
V
T2
V2
CV ln nR ln
T1
V1

Reversible adiabatic
T 2
CV ln
T1

(CV / nR )

T 2
CV ln
T1

(CV

,m

/R)

ln

V 1
, or
V 2

V 1
ln
V 2

Heat capacity ratio and adiabats

If the system is subject to pressure
change pV = constant, = Cp,m/CV,m.

CV ,m R

1 1

CV ,m

p V p2V2

Illustration
Consider adiabatic reversible expansion of
0.020mol, initially at 25C, from 0.50L to 1.00L.
CV,m= 12.48J/K.mol
CV ,m / R 1.501
T 2
ln
T1

11.501

ln

V 1

V 2
1
1.5

0.50L
T 2 298
188 K
1.00L
w ad CV dT 0.020 mol 12.48 J K -1mol-1 -110 K =-27 J

Thermo-chemistry

Standard enthalpy changes

Enthalpies of physical change
Enthalpy of ionization
Enthalpy of bond formation and
dissociation
Enthalpy of chemical changes

Standard enthalpy changes

The standard state of a substance at a given
temperature is its pure form at 1 bar
- standard state of liquid ethanol at 298 K is pure
liquid ethanol at 298 K.
Standard enthalpy of vaporization, vapH is the
enthalpy change per mole when a pure liquid at 1 bar
vaporizes to a gas at 1 bar, as in
H2O(l)

H2O(g)

Standard enthalpy changes

The standard state of a substance at a
specific temperature in its pure form at 1
bar,
H2O(l)

H2O(g)

Standard enthalpy of vaporization,

vap H 40.66 kJ mol-1 at 373K
The conventional T for reporting

vap H

is 298 K

Enthalpies of Physical change

The standard enthalpy change that accompanies a change of
physical state is called the standard enthalpy of transition and
denoted trsH.
vapH, fusH
H2O(s) H2O(l)

fusH(273)=+6.01 kJ/mol

H is a state function independent of path

Consider the conversion of solid to vapor either as occurring
by sublimation

Enthalpies of physical change

fus H

vap H

fus vap

H2O(s)

H2O(l)

H2O(l)

H2O(g)

H2O(s)

H2O(g)

H is a state function
sub H e fus H e vap H e

H is state function: Standard enthalpy

changes of a forward process and its
reverse must differ only in sign

A B H B A
e

Enthalpies of chemical change

r H e

H me

product

H me

reactant

N 2 g 3H 2 g 2 NH 3 g

r H 2 H m NH 3 H m N 2 3H m H 2

c6 H12O6 s 6O2 g 6CO2 6 H 2O l

c H e 2808 kJ/mol

2808 kJ of heat released when 1 mole of burns under

standard conditions.

Standard enthalpies of formation

The standard enthalpy of formation,
of a substance is the standard reaction
enthalpy for the formation of the compound
from its elements in their reference states.
The reference state of an element is
its most stable state at the specified
temperature and 1 bar.

Example
At 298 K the reference state of nitrogen is a gas of N 2(g)
molecules,
see your book for more examples.

f H of elements in their reference state are zero at all

temperatures.
*To calculate the enthalpy of any reaction, use

r H v f H v f H
p

Example

2NH 3 l 2NO g H 2O 2 l 4N 2 g

r H f H H 2O 2 , l 4 f H N 2, g

2 f H NH 3 , l 2 f H NO , g 892.3 KJ

N.B,

H f N 2 , g 0

mol

 r H v f H v f H
p

Example
2NH 3 l 2NO g H 2O 2 l 4N 2 g

r H f H H 2O 2 , l 4 f H N 2, g

2 f H NH 3 , l 2 f H NO , g 892.3 KJ

N.B
H f N 2 , g 0

mol

The temperature dependence of H of the

phase transition
T2

H (T2 ) H (T1 ) C p dT
T1

H (T ) H (0)

T fus

Tb

C p (T )dT fus H C Pl (T )dT

s

T fus

vap H C Pg (T )dT
Tb

The temperature dependence of Hr

T2

H (T2 ) H (T1 ) C p dT
T1

T2

r H (T2 ) r H (T1 ) r C p dT

r C p r C p ,m ( J )

T1

The change in the heat capacity is essentially the difference

Of the molar heat capacities of products and reactants weighed
by the stoichiometric number that appears in the chemical
Reactions.

State fuctions
Exact and inexact differentials:
If a system is taken along a path, by heating, from state i
to state f, U changes from Ui to Uf, and the overall
change is the sum of all infinitesimal changes along the
path:
f

U dU
i

U depends on i and f of the system but is

independent of the path between them. The path

independence of the integral is expressed by saying
.that dU is an exact differential

:Exact Differential
an infinitesimal quantity which when integrated
gives a result that is independent of the path
between the initial and final states.
When a system is heated, the total energy
transferred as heat is the sum of all individual
contributions at each point of the path.
f

i , path

dq

Note the difference between the two equations

(1)q and not q becauseqthe qenergy supplied as heat can not
f
i
be expressed as
(2) must specify the path (if adiabatic, q = 0, whereas a
nonadiabatic path has q 0) of the integration. This pathdependent is defined by saying that q is an inexact
differential. An infinitesimal quantity when integrated
yields a result depends on the path between the initial and
final states. Often dq is written q and dw is written w.

Computing w, q, U
Consider a perfect gas in a cylinder
Initial state:T, Vi
Final state: T, Vf
Path 1: free expansion against pex = 0.
Path 2: reversible, isothermal expansion.
Find w, q, U!

Solution
Internal energy of a perfect gas only depends on
temperature change U 0
:Path 1

U 0

:Path 1 U 0

w q

qw0

V f
w nRT ln q
Vi

U is the same in both paths

Changes in internal energy

.We shall

study the consequences of dU being exact differential

U
U
dT

T V
V

dU

dV
T

This equation means any infinitesimal change in U is

proportional to the infinitesimal changes of V and T, the
coefficients of proportionality being the partial derivatives

T
V T

T
T

U
CV

T V

: internal pressure at fixed temperature

is the measure of the cohesive forces in
the sample.

Changes in Internal Energy U

U
U

dU
dT

T V
V

The partial derivatives

dV
T

CV

U
T

are the proportionality coefficients for the changes in dT and

dV, where T is called internal pressure and Cv the heat
,capacity. Thus

dU CV dT T dV

T is the measure of the cohesive forces in the sample, it is

therefore zero for a perfect gas.

How does the internal energy U change as a

?function of T with the pressure held constant

dU CV dT T dV
divide the above equation by dT, you get

dV
dU

CV T
dT
dT
U

CV T
p

(constant pressure process)

U

V
CV T

Define
1 V

V T

then
U

CV T V
p

where is called expansion coefficient. Large implies

volume of sample is strongly temperature dependent, and
small means that the volume of sample is not responsive
to temperature change.
Example:
1
Find fora perfect
gas.

CV T V (1 / T ) CV

where T = 0.

Temperature Dependence of The Enthalpy

H = U + pV, as H depends on T and p
H
dH

H
dp
dT
p T
p

We need to find the variation of H with T at constant V,

T

Divide both sides of dH by dT,

dH H

dT T

dp
dT

(constant V)

dH

dT

H dp

p
dT
T

Two partial derivatives are unfamiliar here:

H
dp

and

dT
p T

We resort to techniques of calculus to turn those

unrecognizable partial derivatives into familiar ones.

 p
p
V

T |V V T T

T p

V
p

1 V

V T p

1 V
V p
T

1 V

V p

1 V
T

V p T

Calculate
(a) Perfect gas

(b)

nRT
b 1
p
1
V nb
Vm T

(c)

RT
a
p
2
Vm b Vm

T
T V

H p
H

V
T

C p
V

Cp

T V p T T
H
H T

T
T
p
p

H
H

C p
T

H p
C
p

is Joule- Thomson coefficient.

Joule- Thomson Experiment

Example:
1. Find

1
T
V

for perfect gas!

V
nRT 1
1

p
V
p

T
p

The higher the pressure of the gas the lower its compressibility!

2. Find

for

a. a van der Waals gas

RT
b. a gas with this equation
p of state ,
Vm b

1 V
T

V p T
T
p
V

p
T

V p

p Vm b
R

p
T

p R
Vm b

1
1 Vm b R
1 Vm b
R
T
.

P
V
V
R
p
V
p

Joule-Thomson coefficient
H
T

C p
Cp
p T
p
but
H

T
p T

. T is a thermal Joule-Thomson coefficient

T C p
C p

C
1

T p

p
p

T V
T
T

How can one measure T ?

T C p
If we can measure T, we can then divide it
by C p of the gas and get at constant H!

To measure T, we need to study the ratio

of
H
H q p
as p 0
p
and p may be measured

Inversion temperature of gas

Depending the identity of the gas, pressure,
relative
magnitudes
of
attractive
and
intermolecular forces and the temperature, may
be either positive or negative.

If
1. Cooling ( > 0)

T2 T1 0
0

p2 p1 0
T2 < T1 gas is cooler
p2 < p1, it is expansion

2. < 0 (heating)
T2 > T1 upon expansion,
P2 > P 1

Look at N2(g) case:

Each gas got 2 inversion temperatures: Low and high

Deeper Look at
for Van der Waals gas is given by
2a
b

RT

C p ,m

For most gases under ordinary conditions, 2a/RT > b

(attractive forces predominate over repulsive forces)
gas cools upon expansion

At sufficiently high T, the inequality is reversed,

and the gas warms on expansion. The temperature
at which changes sign is called inversion
temperature.

2a
TI
Rb

TI is normally several hundred degrees above

25 C. However, H2(g) and He have TI well below
25 C. This may be attributed to the very small
attractive forces present in these gases.

Boyles temperature is given by TB = a/Rb.

What is the relationship between TI and TB?
For to go from positive to negative, it will
have to pass through = 0 (ideal gas) and
every gas behaves ideally at TB inversion
temperature is when gas is ideal and = 0.

The relation between CV and CP

From before, for a perfect gas
CP - CV = nR

The relation for a nonperfect gas is given by (see

text for proof)
a 2TV
C P - CV =
kT