First Law

Physical Chemistry
Summary
Ideal Gases/Perfect Gases

Key Notes
Gases: a fluid which has no intrinsic shape, and which
expands indefinitely to fill any container in which it is held.
The ideal gas equations: the relations among the amount
of gas substance, temperature, pressure and volume.
PV = nRT
PVm = RT
Vm: molar gas volume

2
Physical
Chemistry
Summary
Ideal Gases/Perfect Gases
Key Notes
Partial pressure: the pressure exerted by each component
in a gaseous mixture.
Px = nxRT/V
nx: mole
Pi = xiPtotal
xi: mole fraction
Daltons law: the total pressure exerted by a mixture of

ideal gases in a volume is equal to the arithmetric sum of
the partial pressures.
Ptotal = ntotalRT/V
3
Chapter 2
CHAPTER 2
The First Law of Thermodynamics
Basic Concepts
Isothermal:
A system which is held at constant
temperature
Adiabatic: A system in which energy may
be transferred as work, but not as heat.
Diathermic: A system which allows energy to
escape as heat through its boundary if there is a
difference in temperature between the system
and its surroundings.
Internal Energy
Chapter 2
Internal energy: Total amount of energy

in a system. The sum total of all kinetic and
potential energy within the system.
Internal energy changes: The sign of U
Negative values: a system loses energy to
the surroundings
Positive values: a system gains energy from
the surroundings
5
Physical
Chemistry
Chapter 2
Thermodynamic Properties of system

Extensive property The value of the property
changes according to the amount of material
which is present (e.g., mass, volume, internal
energy)
Intensive property independent of the amount
of
material
which isthe
present
(e.g.,
temperature,
State
functions:
value of
a particular
density)
property for a system depends solely on the
state of the system at time (e.g., pressure,
volume,
internal energy,
entropy)
Path functions:
A property
depends upon the
path by which a system in one state is changed
into another state (e.g., work, heat)
6
Chapter 2
Work
Work: the transfer of energy as orderly
motion
due to energy being expanded against an
opposing force (in mechanical terms)
dw Fx
(2.10)*
dx
Reversible P-V Work
dwrev = -PdV
closed system, reversible process
wrev 2 PdV
1
(2.30)
*
closed system, reversible process
(2.31
) 7
Chapter 2
Reversible P-V
dx
V
Work
Fx=F=PA
Piston moving
(a) Expansion (dV >
0)
dx
V
Fx=F=PA
Piston moving
(b) Compression (dV
< 0)
Chapter 2
Heat: the transfer of energy as disorderly

motion as the result of a temperature difference
between the system and its surroundings.
exothermic: a process that releases energy
as heat (all combustion reactions)
endothermic: processes that adsorb energy
as heat
(the vaporizationan
of adiabatic
water)
system
(a) an
endothermic
process
(a)
(b) an
exothermic
process
(b)
Chapter 2
Heat: the transfer of energy as disorderly

motion as the result of a temperature difference
between the system and its surroundings.
endothermic: energy enters as heat from
the surroundings, the system remains at the
same
T (c)
exothermic:
energy leaves as heat from the
system, the system remains at the same T (d)
a diathermic container
Heat
(c)
An
isothermal
process
Heat
(d)
10
Physical
Chemistry
Chapter 2
Heat
Two bodies at unequal temperatures are placed in contact
m1, c1, T1
m2, c2, T2
(T2>T1)
m2 c2 (T2 T f ) m1c1 (T f T1 ) q
Specific heat capacity
Tf
T1<Tf<T2
(2.34)
11
Chapter 2
Heat
m2 c2 (T2 T f ) m1c1 (T f T1 ) q
dqP mcP dT
(2.34)
(2.35)
T2
qP m C P (T )dT
closed syst., P const.
T1
dqP
CP
dT
(2.36)
(2.37)
T2
Tf
Tf
T1
m2 cP2 (T )dT m1 cP1 (T )dT qP
(2.38)
12
Chapter 2
The First Law of Thermodynamics

The total energy of an isolated thermodynamic
the conservation of
system is constant
energy
Energy cannot be created or
destroyed
U = q + w
(2.41)
*
Closed system at rest in the absence of
external
fieldssupplied to the
q is the heat
system
w is the work done on the system
U is the internal energy of the
13
Chapter 2
Heat and
Work
Both are measures of energy
transfer, and both have the same
units
as energy.
The unit
of heat can be defined in
terms of joule.
1 cal 4.184 J
(2.44)*
The calorie defined by (2.44) is

called thermodynamical calorie, calth
14
Chapter 2
Enthalp
H U PV
(2.45)*
Since U, P, V are state functions, H is a state

function.
Let qP be the heat adsorbed in a constantpressure process in a closed system, from
V2
the first law
U U 2 U1 q w q PdV
V1
V2
q p P dV qP P (V2 V1 )
V1
qP U 2 PV2 U1 PV1
(U 2 P2V2 ) (U1 P1V1 ) H 2 H1
P1=P2=P
H q P at cons P,closed syst. P-V
(2.46)
work only
15
Chapter 2
Enthalp
H U PV
(2.45)*
For any change of state, the enthalpy

change H
H H 2 H1 (U 2 P2V2 ) (U1 P1V1 ) U ( PV )
(2.47)
H U PV
at constant P
U and V are extensive, H is
(2.48)
extensive.
The molar enthalpy of a pure
substance
Hm
H U PV
U m PVm
n
n
16
Physical
Chemistry
Enthalp
Chapter 2
Let qV be the heat adsorbed in a constantvolume process in a closed system, if it can

do only P-V work, then
dw = - PdV = 0
Since dV = 0
Then dw = 0
So w = 0
U q w
From the first
law
U qV (closed syst., P-V work only, V
(2.49)
const.)
17
Chapter 2
Enthalp
y
H U PV
at constant P
(2.48)
For a reaction involving a perfect

gas
Example
H U nRT
CaCO3 ( s ) CaO ( s ) CO2 ( g )
n 1
(1 mole of gaseous CO2 is created)
H U nRT U RT U 2.48kJmol 1
at 298
K
18
Chapter 2
Exothermic and Endothermic

Heat change in system Process
Value of H
Heat loss
(heat lost to the
surroundings)
Heat gain
(heat gained from the
surroundings)
Negative
(H < 0)
Exothermic
Endothermic Positive
(H > 0)
The sign of enthalpy change indicates the

direction of heat flow
19
Chapter 2
Heat
CapacitiesC
dq pr
(2.50)*
pr
dT
heat capacity at constant pressure CP
(isobaric heat capacity)
dqP
CP
(2.51)*
dT
heat capacity at constant volume CV
(isochoric heat capacity)
dqV
CV
dT
(2.52)*
20
Chapter 2
Heat
CapacitiesC
pr
dq pr

dT
(2.50)*
dqP
CP
dT
(2.51)*
dqV
CV
dT
(2.52)*
U
H
C
CP
V
(2.53)*
V
T P
CP and CV give the rates of change of H
and U with temperature T.
21
Chapter 2
Heat
The slope of the curve at any
Capacities
constant volume heat
temperature
capacity (isochoric heat

capacity) CV
U
CV
T V
dU CV dT
U
A
U CV T qV
U qV
T
(2.49)
22
Chapter 2
Heat
The slope of the H-T curve at any
Capacities
temperature
constant
pressure heat
capacity (isobaric heat
capacity) Cp
H
H
CP
T P
dH C P dT
B
A
H C P T qP
H q P
T
(2.46)
23
Chapter 2
The relation between CP and

dH CHV
CP
dT
dU U
CV
dT T
H
C P CV
T
p
U
C P CV
V
P
T
p
(U PV )
T
p
T
p
(2.57)
V
24
Chapter 2
C P CV
V
U
T P T
U
dV
V T
P
P
d
T
dU
(2.57)
V
(2.58)
At constant P
U
U
dU P
dTP
dVP
T V
V T
dU P U
dTP T
U
dV P
dTP
U V
V T T
Substitution of (2.59) into (2.57)

U
V
CP CV
P
V T
T
(2.59
)
(2.60)
25
Chapter 2
U
V
CP CV
P
V T
T
Why? CP CV
(2.60)
P
dqP
CP
dT
dqV
CV
dT
dU dq dw
(first law)
dq dU dw dU PdV
dqP dU P PdVP
dqV dU V
dqP dqV dU P dU V PdVP
(2.61)
26
Chapter 2
dq P dqV dU P dU V PdVP
(1) In a constant pressure process, part of the
added heat goes into the work of expansion
(2) dU P dU V
U
V
CP CV
P
V T
T
internal pressure
(2.61)
C P CV
(2.60)
P
intermolecular potential energy

27
Chapter 2
Joule experiment
Chamber A: filled with a gas
Chamber B: is evacuated
Valve: is closed
Valve: is opened
Chamber A: releases a gas
Chamber B: filled with a gas
thermometer
Adiabatic wall
valve
A
Fig. 2.6
After equilibrium is reached

The temperature change in the system is measured by the
thermometer.
28
Chapter 2
Joule experiment
q = 0 (the system is surrounded by adiabatic walls)
w = 0 (gas expansion into a vacuum)
U = q + w = 0 + 0 = 0 (a constant-energy process)
The experiment measures T
with V at constant internal
energy, T
V U
thermometer
Adiabatic wall
Joule coefficient
T
J
valve
(2.62)
U
Fig. 2.6
B 29
Chapter 2
T
J
Joule experiment
V
total differential of z(x,y)
(2.62)
U
z
z
dy
dz
dx
x y
y x
(1.30)*
total differential of z(r,s,t)

z
dz
z
dr
s
s ,t
z
ds
t
r ,t
When y is kept constant
z
dz y
dx y
x y
dt
r ,s
When x is kept constant

(1.31)
z
dy x
dz x
y x
30
Chapter 2
Joule experiment
Division by dzy gives
z
1
T
J
(2.62)
U
dx y
y
z x
dz y x y z
From the definition of the partial derivative

z
x z
(1.32)*
y
z
z
dy (1.30)*
dz
dx
When z stays constant
x y
y x
z
z
dy z
0
dx z
(1.33)
y
31
Chapter 2
T
J
Joule experiment
(2.62)
U
Division by dyz gives

z
0
dx z z

dy z y
y y
z
0
x
z
y
y y z
1
(y
)x
Using (1.32) with x and y interchanged and multiplied by

z
x y z
y z z x x
1
y
(1.34)*
32
Chapter 2
T
J
Joule experiment
(2.62)
U
Replaced x, y, z with T, U, and V, gives
T U V
U V V T T
U
T

U V
1
U
1
U T

T V V
When (1.32), (2.53) and (2.62) were used
CV J
T
(2.63)
33
Chapter 2
Joule-Thomson experiment
Adiabatic Wall
Porous Plug
B
P1
P1, V1,
T1
P2
P1
P1
(a)
P2 < P1
P1
P2, V2,
T2
P2
P2
P2
(b
)
(c)
Fig. 2.7 The Joule-Thomson experiment.
34
The slow throttling of a gas through a rigid, porous Chapter 2

plug. The system is enclosed in adiabatic walls. The
left piston is held at a fixed pressure P1, the right
piston is held at a fixed pressure P2 (<P1).
The partition B is porous but not greatly so. This allows
the gas to be slowly forced from one chamber to the other.
Because the throttling process is slow, pressure
equilibrium is maintained in each chamber. Essentially all
the pressure drop from P1 to P2 occurs in the porous plug.
B
P1
P2
P1, V1,
T1
P1
P1
(a)
P1
P2 < P1
P2, V2,
T2
P2
P2
P2
(b
)
(c)
35
Joule-Thomson experiment
Chapter 2
The work done on the gas in throttling it through the plug

w P1V1 P2 V2
q 0 (adiabatic process)
U2 - U1 q + w w P1V1
PU
2 V
2
P2 V2 U1 P1V1
2
H2 H1
or
H 0
Joule-Thomson coefficient
JT
(2.64)*
H
36
Chapter 2
Example:
Calculate 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 oC.
In (a) the volume cannot change, so no work is done
w P V 0
In (b) the gas gives back the atmosphere and therefore
w P V
nRT
V V f Vi V f
Pex
nRT
w P
nRT
P
The amount of
H2 produced
37
Chapter 2
Example:
Calculate 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 oC.
The reaction is
Fe( s ) 2 HCl (aq) FeCl2 (aq) H 2 ( g )

1 mole H2 is generated when 1 mole Fe is consumed
50 g
1
1
w
(
8
.
3145
JK
mol
) (298.15 K ) 2.2kJ
1
55.85 gmol
Molar mass of Fe
The system does 2.2 kJ of work

driving back the atmosphere
38
Chapter 2
A perfect gas
Reversible isothermal process in a
perfect 2gas
2 dV
nRT
w PdV
dV nRT
1
1
1 V
V
nRT (ln V2 ln V1 )
2
Reversible adiabatic process in a

perfect gas
(2.74)
nRT
CV dT PdV
dV
V
RT
CV ,m dT
dV
V
2 CV , m
2 R
V1
1 T dT 1 V dV R(ln V2 ln V1 ) R ln V2 (2.75)
39
A perfect gas
CV , m
Chapter 2
R
V1
dT dV R (ln V2 ln V1 ) R ln
(2.75)
1
T
V
V2
2
If CV,m is constant (independent of T over

a wide temperature range)
2
T2
CV , m
1
dT CV , m T dT CV ,m ln
1
T
T1
T2
V1
R ln
CV ,m ln
T1
VR 2
T2
V1 CV ,m
ln
ln
T1
V2
R
T2 V1 CV ,m

T1 V2
Reversible adiabatic process, CV is
(2.76)
40
Chapter 2
A perfect gas
T2 V1

T1 V2
R
CV ,m
(2.76)
An alternative equation can be obtained

by using
P1V1 P2V2
T1
T2
P2V2 V1

P1V1 V2
R
CV ,m
1 R / CV , m
P1V1
1 R / CV , m
P2V2
41
A perfect gas
Chapter 2
T2 V1

T1 V2
R
CV ,m
(2.76)
CP,m - CV,m = R
(2.72)*
CV ,m R C P ,m
R

1

CV ,m CV ,m CV ,m
CV , m R C P, m
C P ,m
Heat capacity
CV ,m
ratio
1 R / CV , m
1 R / CV , m
P1V1
P2V2
P1V1 P2V2
U q w w
U CV (T2 T1 ) w
(2.77)
dU CV dT
(2.78)
42
Thermodynamic
Key
Notes
Processes
Chapter 2
final
initial
cyclic
1. Cyclic process: the systems final state is the same as the

initial state.
2. Reversible process: the system is always infinitesimally
close to equilibrium, and an infinitesimal change in
conditions can restore both system and surroundings to
their initial state.
3. Isothermal process: temperature is held constant
throughout the process.
4. Adiabatic process: dq=0 and q=0
5. Isochoric (isobaric) process: volume (pressure) is held
constant throughout the process.
43
Chapter 2
Calculation of First-Law
Quantities
1. Reversible phase change at constant T and P:
P:
2. Constant-pressure heating with no phase change:
3. Constant-volume heating with no phase change:
4. Perfect-gas change of state:
5. Reversible isothermal process in a perfect gas
6. Reversible adiabatic process in a perfect gas:
7. Adiabatic expansion of a perfect gas into vacuum.
44
Chapter 2
Quantities
1. Reversible phase change at constant T and
P:
2
w PdV PV
1
( PV nRT )
H qP q
U q w
45
Chapter 2
Quantities
46
Chapter 2
Quantities

2
w wrev PdV PV
1
T2
H qP C P (T )dT
T1
(2.79)
U q w qP w
47
Chapter 2
Quantities
48
Chapter 2
Quantities

w0
2
U q w CV dT qV
1
(2.80)
H U ( PV ) U VP
49
Chapter 2
Quantities
50
Chapter 2
Quantities

T2
T2
T1
T1
U CV (T )dT , H C P (T )dT
T
wrev PdV nR dV
1
1 V

q U w
2
(2.81)
51
Chapter 2
Quantities
52
Chapter 2
1. Reversible Quantities
phase change at constant T and P:
U 0
H 0
2
V2
w PdV nRT ln
(2.74)
1
V1
q w
(q w U 0)
53
Chapter 2
Quantities
54
Chapter 2
Quantities
1. Reversible phase
change at constant T and P:
2.
3.
4.
5.
6.
Constant-pressure heating with no phase change:

Constant-volume heating with no phase change:
Perfect-gas change of state:
Reversible isothermal process in a perfect gas
Reversible adiabatic process in a perfect gas:
q0
T2
T2
U CV (T )dT , H C P (T )dT
T1
T1
(2.81)
(q w U )
CP

P1V1 P2V2
CV
w U
(CV const.)
55
Chapter 2
Quantities
56
vacuum.
Chapter 2
Quantities
1. Reversible phase
change at constant T and P:
2.
3.
4.
5.
6.
7.
Constant-pressure heating with no phase change:

Constant-volume heating with no phase change:
Perfect-gas change of state:
Reversible isothermal process in a perfect gas
Reversible adiabatic process in a perfect gas:
Adiabatic expansion of a perfect gas into
vacuum.
q0
w0
U q w 0
H U ( PV ) U nRT 0
57
Chapter 2
Molecular interpretation of
heat and work
Heat is the transfer of energy that makes use of chaotic
molecular motion (thermal motion)
Heat is identified as energy transfer making use of thermal
motion in the surroundings
Work is the transfer of energy that makes use of organized
motion
Work is identified as energy transfer making use of the
organized motion of atoms in the surroundings
58
Chapter 2
Molecular interpretation of
heat and work
System
System
(a) Work
(b) Heat
In a uniform manner
In a chaotic manner
59
Chapter 2
The molecular nature of internal

The internal energy isenergy
energy at the molecular level.
gas: CO2
moves the
same distance
O
C
O
in the same
A translation
direction
The spatial orientation changes,
but the distances remain fixed
O
C
O
A rotation
the atoms
oscillate about
their equilibrium
O
C
O
positions
A vibration
60
Fig. 2.14
Chapter 2
The internal energy

Transnational energy, Utr
Rotational energy, Urot
Vibrational energy, Uvib
Electronic energy, Uel
Energy due to intermolecular forces, Uintemol
Rest-mass energy of the electrons & nuclei,
Urest
61
Chapter 2
The internal energy
For a gas or liquid, the molar internal energy
U m U tr ,m U rot ,m U vib ,m U el ,m U int ermol ,m U rest ,m
constant
f (T )
For a perfect gas

3
RT
2
Um
3
RT U vib ,m (T )
2
(RT )
constant
f (T , P )
No chemical reactions
T is not extremely high
0 constant
3
3
RT RT ( RT ) U vib ,m (T ) const.
2
2
Perf. gas
(2.88)
62

First Law

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First Law

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Physical Chemistry

Ideal Gases/Perfect Gases

Vm: molar gas volume

Ideal Gases/Perfect Gases

xi: mole fraction

Daltons law: the total pressure exerted by a mixture of

Internal energy: Total amount of energy

Thermodynamic Properties of system

closed system, reversible process

closed system, reversible process

Heat: the transfer of energy as disorderly

Heat: the transfer of energy as disorderly

Two bodies at unequal temperatures are placed in contact

closed syst., P const.

m2 cP2 (T )dT m1 cP1 (T )dT qP

The First Law of Thermodynamics

U is the internal energy of the

The calorie defined by (2.44) is

Since U, P, V are state functions, H is a state

For any change of state, the enthalpy

Let qV be the heat adsorbed in a constantvolume process in a closed system, if it can

For a reaction involving a perfect

(1 mole of gaseous CO2 is created)

Exothermic and Endothermic

The sign of enthalpy change indicates the

capacity (isochoric heat

The relation between CP and

Substitution of (2.59) into (2.57)

intermolecular potential energy

After equilibrium is reached

total differential of z(r,s,t)

When y is kept constant

When x is kept constant

From the definition of the partial derivative

Division by dyz gives

Using (1.32) with x and y interchanged and multiplied by

Replaced x, y, z with T, U, and V, gives

When (1.32), (2.53) and (2.62) were used

Fig. 2.7 The Joule-Thomson experiment.

The slow throttling of a gas through a rigid, porous Chapter 2

The work done on the gas in throttling it through the plug

Fe( s ) 2 HCl (aq) FeCl2 (aq) H 2 ( g )

The system does 2.2 kJ of work

Reversible adiabatic process in a

If CV,m is constant (independent of T over

An alternative equation can be obtained

1. Cyclic process: the systems final state is the same as the

1. Reversible phase change at constant T and P:

1. Reversible phase change at constant T and P:

1. Reversible phase change at constant T and P:

Constant-pressure heating with no phase change:

Constant-pressure heating with no phase change:

The molecular nature of internal

The internal energy

The internal energy

For a gas or liquid, the molar internal energy

U m U tr ,m U rot ,m U vib ,m U el ,m U int ermol ,m U rest ,m

For a perfect gas

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