Physical chemistry lecture on gases and thermodynamics

8/20/2014
Physical Chemistry
Lecture no. 1
ChE Course Integration 1 Review
Sherrie Mae S. Medez
Powerpoint Templates
Page 1
OUTLINE
BASIC CONCEPTS
integration and differentiation
partial derivatives
functions of multiple variables
GASES
definition and properties
ideal gases
kinetic molecular theory of gases
mixture of ideal gases
real gases
THERMODYNAMICS
basic concepts
laws
Page 2
8/20/2014
OUTLINE
LIQUIDS
characteristics
physical properties
SAMPLE PROBLEMS
Page 3
GASES
Page 4
8/20/2014
GASES
Simplest forms of matter
Properties:
Fill the volume of the container
Less dense than solids or liquids
Have highly varying densities, depending on
the condition
Readily mix with other gases
Have volumes that change with
change in temperature
Page 5
Source: http://www.phy.cuhk.edu.hk/contextual/heat/tep/trans01_e.html
The Perfect / ideal gas

a collection of atoms or molecules having
continuous random motion
speeds of the molecules are increased as
temperature is raised
differs from liquids because except during
collisions, molecules are far from one another
and are not significantly affected by
intermolecular forces
Page 6
8/20/2014
The ideal gas law

Defines the state of a PURE GAS
PV nRT
Equation of state interrelates the 4
variables that define the state of a
gas
P = f(n,V,T)
Page 7
The ideal gas law
PV nRT
where P = pressure
V = volume
n = no. of moles
T = temperature
R = universal gas constant
= 0.08206 atm L/ (mol-K)
= 8.314 J/(mol-K)
Page 8
8/20/2014
The ideal gas law variables

1) PRESSURE
F
P
A
Force (can also be weight)

Area to which the force is
applied
- the force comes from the ceaseless motion

of the gases onto the walls of the container
- these collisions are numerous that they
exert an EFFECTIVE STEADY FORCE, and
therefore an EFFECTIVE STEADY PRESSURE
Page 9

1) PRESSURE
F
P
A
Force (can also be weight)

Area to which the force is
applied
- units: atm, Torr, bar, mmHg, Pascal, psi

1 atm = 760 Torr
= 760 mmHg
= 101325 N/m2
= 1.01325 bar
= 14.7 psi
Page 10
8/20/2014

1) PRESSURE
Physical Illustration of pressure:
Consider:
- movable
Pright
wall will continue to move until Pleft =
- when movable wall stops moving, then

MECHANICAL EQUILIBRIUM (equality of
pressure) is achieved
Page 11

1) PRESSURE
* Manometer used to measure
the pressure of a gas inside a
container
Source: http://www.efunda.com/formulae/fluids/images/Manometer_A.gif
Page 12
8/20/2014

2) TEMPERATURE
- physical change that can be observed when 2
objects come into contact with one another
units: Celsius, Fahrenheit
Kelvin, Rankine
Physical Illustration of temperature:

* Diathermic wall exists when 2 objects of
different temperatures come into contact
and change is observed
- if no change is observed, then there is an

ADIABATIC WALL
* Temperature is a property that indicates the
direction of the
flow of energy
through a thermally Page 13
Powerpoint
Templates
conducting rigid wall

2) TEMPERATURE
*When the diathermic wall stops transferring

heat, then THERMAL EQUILIBRIUM (equality
of temperature) is achieved
Page 14
8/20/2014

2) TEMPERATURE
Zeroth Law of Thermodynamics
A
B
If A is in thermal equilibrium with B,

and B is in thermal equilibrium with
C, then A is in thermal equilibrium
with C.
-This law allows for the consideration of temperature

as a state function.
-Basis of thermometers systems that contain
substances which expand when heated (e.g.
mercury)
Page 15
The gas laws

1) Boyles Law
PV = constant
P1 V1 = P2 V2
2) Charles Law / Gay-Lussacs Law
V = constant x T
V1 V2
T1 T2
3) Alternative to Charles Law

P = constant x T
P1 P2
T1 T2
Page 16
8/20/2014
The gas laws
Page 17
The gas laws

4) Avogadros Principle
V = constant x n
- at a given temperature and pressure, the volume
per mole of a gas is the same regardless of the identity
of the gases
5) The ideal gas law
PV = constant x nT
Vm
V
n
PV nRT
- gases obey this at low pressure and high temperature

6) Combined gas equation at constant n
PV
PV
1 1
2 2
T1
T2 Templates
Powerpoint
Page 18
8/20/2014
The gas laws
Page 19
Conditions:
STANDARD AMBIENT TEMPERATURE AND
PRESSURE (SATP)
= 298 K, 1 bar
Vm = 24.789 L/mol
STANDARD TEMPERATURE AND PRESSURE
= 00 C or 273.15 K, 1 atm
Vm = 22.414 L/mol
Page 20
10
8/20/2014
Mixtures of ideal gases

In a mixture of ideal gases, each
component contributes to the total
pressure of the system
Page 21

DALTONS LAW OF PARTIAL
PRESSURES
The pressure exerted by a mixture
of gases is the sum of the partial
pressure of the gases.
pT p A pB pC
pi
ni RT
V
where pT = total pressure

Page 22
11
8/20/2014

DALTONS LAW OF PARTIAL
PRESSURES
in terms of molar fraction:
xi
ni
nT
nT nA nB ...
for a mixture xA xB xc ... 1.0

partial pressure can be expressed
as:
the pressure that will be

exerted by a gas if it were
alone in a container
pi xi pT
pA pBPowerpoint
xB.... ) pT pT
Templates
... ( xA
Page 23

GRAHAMS LAW
d g1
dg 2
uavg1
uavg 2
MWg 2
MWg1
Obtained from the experiment:

NH3(g) + HCl(g) NH4Cl(s)
Page 24
12
8/20/2014

AMAGATS LAW OF COMBINING
VOLUMES
The total volume occupied by a mixture of
gases is equal to the sum of the volumes
which would be occupied by each
constituent at the same temperature and
pressure as the mixture.
vT v A vB ...
vi
nTemplates
i RT
vPowerpoint
T
P
ni RT
P
Page 25

AMAGATS LAW OF COMBINING
VOLUMES
vf
v ft
for gases,
vi
vm
vm
v fi xi
Page 26
13
8/20/2014
Variation of atmospheric pressure

with altitude
p = po eh/H
Where p0 pressure at sea level
h altitude
H RT/Mg
p pressure at altitude h
Page 27
Kinetic molecular theory

of gases
Is the theoretical means of
displaying the behavior of gases
and all assumptions associated
with them
First proposed by Bernoulli in 1738
Page 28
14
8/20/2014

of gases
POSTULATES:
1) Gases are composed of minute discrete
particles called molecules. All molecules of
1 gas are of the same mass and size, but
differ from gas to gas.
2) The molecules within a container are
believed to be in ceaseless, chaotic
motion during which they collide with
each other and with the walls of the
container.
Page 29

of gases
POSTULATES:
3) The bombardment of the container walls by the
molecules gives rise to the phenomenon we call
PRESSURE. (The average force on the walls
per unit area is the average force per unit area
which the molecules exert in their collisions with
the walls).
4) Inasmuch as the pressure of a gas within a
container does not vary with time at any given
pressure and temperature, the molecular
collisions must involve no energy loss due to
friction. In other words, all molecular collisions
are elastic.
Page 30
15
8/20/2014

of gases
POSTULATES:
5) The absolute temperature is a quantity
proportional to the average kinetic energy
of all the molecules in a system.
6) At relatively low pressures, the average

distances between molecules are large
compared with the molecular diameters,
and hence the attractive forces between
molecules, which depend on the distance
of molecular separation, may be
considered negligible.
Page 31

of gases
POSTULATES:
7) Since molecules are small
compared with the distances
between them, their volume may be
considered to be negligible
compared to the volume of the gas
* Postulate nos. 6 and 7 make the
theory limited to IDEAL GASES.
Page 32
16
8/20/2014
Speeds of gas molecules

Most probable speed, Vp
Mean speed, V
Root mean squared speed, Vrms
vp
2 RT
MW
8RT
( MW )
vrms
3RT
MW
*In reality, speeds of molecules span over a wide range ,

Powerpoint
Templates
Page 33
given by the MAXWELL
SPEED
DISTRIBUTIONS.
Maxwell speed
distrIbutions
Page 34
17
8/20/2014
Maxwell speed
distrIbutions
The Maxwell Speed Distributions
depend on the temperature or
molecular weight
Low T or high MW
Intermediate T or MW
High T or low MW
Page 35
Collision frequency
vrel N
V
Where
= collision cross section
vrel = (2)v
V=volume
N = no. of molecules
Mean Free Path
Where
v = mean speed
z = collision frequency
Page 36
18
8/20/2014
Kinetic energy of translation

KE
3
nRT
2
KE
3
RT
2
KE
3
kT
2
Where
k = 1.38066 x 10-23 J/K
= R/N
(Boltzman Constant)
N = Avogadros number
Page 37
Real gases
Gases that do not obey ideal gas laws
exist at low temperature and high pressure, especially
when gases are at the point of condensing to a liquid
INTERMOLECULAR FORCES
REPULSIVE FORCES assist expansion
- Very significant at high pressures
ATTRACTIVE FORCES assist compression
- Very significant at moderate pressures
Low pressure: no significance, volume is high
Moderate pressures: AF > RF
High pressures: RF > AF
Page 38
19
8/20/2014
Compression factor, z
Z
Vm
Vm0
Molar volume
Molar volume of perfect gas
At given T and P,
PVm RTZ
Low P: Z=1
Moderate P: Z<1
High P: Z>1
Page 39
Van der waals equation of state

Applies to real gases
Considers the volume occupied by the
molecules themselves and the attractive
forces between them
The Van der Waals equation:
nRT
n2a
2
V nb V
where
Where Tc and Pc,

are critical
constants
27 R 2Tc2
a
64 Pc
RTc
8 Pc
Page 40
20
8/20/2014
OTHER EQUATIONS OF STATE

1) Kamerlingh Onnes Equation
- expresses PV as a function of a power series
of the pressure at any given temperature
PVm A BP CP2 DP3 .....
where A, B, C, and D are virial coefficients

at low P, only A is significant (A=RT)
2) Berthelot Equation
- applicable for gas pressures <= 1 atm
9 PTc
6T 2
PV nRT 1
(1 2c )
T
c
128PT
Page 41

3) Beattie- Bridgeman Equation
- for wide ranges of temperature (up to -1500
C and 100 atm)
RT
2 3 4
Vm Vm Vm Vm
RT
P
P2
Vm
P RT ( RT )2 ( RT )3
where
RTBo Ao
Rc
Tc2
RTBob Ao a
RBobc
T2
Powerpoint
Templates
Rc Bo
T2
Page 42
21
8/20/2014

4) Virial Equation
PVm RT (1
B C
...)
Vm Vm2
Where B, C, . Are virial coefficients

* the terms in the parenthesis can
be identified with the compression
factor Z
Page 43
CONDENSATION
Critical Temp, Tc: 31.40 C
Critical Pressure, Pc : 72.9 atm
Critical Molar Volume, Vc :0.094 L/mol
Below Tc : condensation
occurs
Page 44
22
8/20/2014
Vapor pressure
Established between the liquid and vapor
phases contained in a sealed volume
the pressure of a vapor above the liquid that
evaporated from the liquid and remains
above the sample in a sealed container
Saturated Vapor Pressure: established at

equilibrium
- increases constantly with temperature
- H2O: 23.76 mmHg at 250C; 760 mmHg at
1000C
Page 45
Critical constants
Critical constants are constants for different gases.
At critical conditions, the physical properties of
the liquid and vapor become identical, and there
is no distinction between the 2 phases
At the critical point, T=Tc , V=Vc, and P = Pc
At points above and at Tc , the substance remains
as a gas.
If T>Tc , a single phase, denser fluid is present,
known as a supercritical fluid.
Page 46
23
8/20/2014
Principle of corresponding
states
At any given values of Tr and Pr , all
liquids should have the corresponding
volumes Vr
Pr
P
PC
Vr
V
VC
Tr
T
TC
substituting into the VDW equation of

state:
3
Pr 2 3Vr 1 8Tr
Vr
Page 47
THERMODYNAMICS
Page 48
24
8/20/2014
Thermodynamics
power developed from heat
the physical science concerned with the
transformation of energy
concerned with heat transfer
e.g. energy released
Provide heat
Provide mechanical work
Provide electricity
Page 49
Thermodynamics
The 1st and the 2nd laws have no
mathematical sense; their validities
are due to no contradictory principles
Thermodynamics can be used for:

1) prediction of the possibility of the
process taking place
2) quantification of needed energy
and maximum yield
Page 50
25
8/20/2014
Thermodynamics
Thermodynamics cannot be used for:
1) establishing reaction rates
Thermodynamic variable?
force
rate driving
resis tan ce
YES
NO
2) revealing microscopic aspects since

it is macroscopic in nature
Page 51
Basic concepts
1) SYSTEM body of matter that serves as the focus of
attention
- types depend on the quantity allowed to be
exchanged through its boundary
TYPE
ENERGY
MATTER
OPEN
CLOSED
ISOLATED
* Adiabatic system that is thermally isolated from the

surroundings
2) SURROUNDINGS the region outside the system
3) BOUNDARY portion separating the system from the
surroundings
Page 52
26
8/20/2014
Basic concepts
4) CONTACT
a) MECHANICAL CONTACT
- present between a system
and its surroundings if a change
in pressure in the surroundings
results to a change in the system
b) THERMAL CONTACT
- present if a change in the
temperature of the surroundings
results to a change in the
temperature of the system
Page 53
Basic concepts
5) WORK
- fundamental physical property in
thermodynamics
W F d
where F = opposing force

d = distance
6) ENERGY
- capacity to do work
* INTERNAL ENERGY- motions, interactions,
bonding of molecules
* KINETIC ENERGY
* POTENTIAL ENERGY
Page 54
27
8/20/2014
Basic concepts
7) EQUILIBRIUM
-static condition or the absence of any
tendency towards change
CHARACTERISTICS:
a. the system does not vary with time
b. the system is uniform (no change in P,
V, T, and concentration
c. the mass, heat, and work flows
between the systems and the
surroundings are equal to zero
d. the rate of all chemical reactions is zero
Page 55
Basic concepts
7) EQUILIBRIUM
-static condition or the absence of any
tendency towards change
i) MECHANICAL EQUILIBRIUM
- between 2 subsystems of equal
pressure
ii) THERMAL EQUILIBRIUM
- between 2 subsystems of equal
temperature
Page 56
28
8/20/2014
Basic concepts
8) PHASE
-homogenous, physically distinct,
mechanically separable portion of a
system
- may or may not be continuous
* Heterogenous 2 or more phases
* Phase rule used to treat heterogenous
equilibria
- fix the number of variables involved
Page 57
Basic concepts
8)
PHASE
Gibbs Phase Rule
- applies to systems in equilibrium
F 2 N
where F - degrees of freedom
- the number of intensive variables
that can be changed without
disturbing the number of phases in equilibrium
- no. of phases
N no. of components / species
Page 58
29
8/20/2014
Basic concepts
9) EXTENSIVE vs INTENSIVE PROPERTY
a) Extensive property dependent on
the amount of substance present
e.g. mass, volume
b) Intensive property independent on
the amount of substance present
e.g. density, molar volume,
temperature
Page 59
Basic concepts
10) STATE vs PATH FUNCTIONS
a) State functions variables that do
not depend on the undertaken from
the initial to the final state
b) Path functions variables that are
dependent on the path taken from the
initial to the final states
Page 60
30
8/20/2014
Zeroth law of thermodynamics

If A is in thermal equilibrium with B
and B is in thermal equilibrium with C,
then A and C are in thermal
equilibrium.
Page 61
Definition and mathematical

statement of the First law
Law of conservation of energy
The energy of the universe is constant.
Energy can neither be created no
destroyed, only transformed from one
form to another.
MATHEMATICAL STATEMENT
For a closed system:
U Q W
Page 62
31
8/20/2014
Definition and mathematical

statement of the First law
MATHEMATICAL STATEMENT
For a closed system:
U
State function
Q W
Path functions
where Q heat
(+) absorbed by the system
(-) absorbed by the
surroundings
W work
(+) done on the system
(-) done by the system
U change in internal energy
Units: 1 calorie
(cgs) = 4.184 J (SI)
Page 63
Internal Energy, U
The total energy of a system
Sum of the total kinetic and
potential energies of the system
U = Uf - Ui
State function, extensive property
Page 64
32
8/20/2014
WORK
Defined as mechanical or P-V work
The transfer of energy that makes use
of organized motion
Source: Physical
Powerpoint
Chemistry
Templates
8th ed by Atkins
Page 65
Work, W
1) By free expansion
pex = 0, therefore W =
2) Against constant external pressure,
pex
Source: Powerpoint
Physical Chemistry
8th ed by Atkins
Templates
Page 66
33
8/20/2014
Enthalpy
The thermal changes at constant
pressure
H U PV
A state function, since U and PV are
also state functions
H H 2 H1
H U PV
H nC p dT
Page 67
Specific Heat
The heat required to raise the
temperature of a unit mass of a
substance by 1 degree of
temperature
U
At constant volume:
Cv
T V
At constant pressure:
H
Cp
T p
For idealPowerpoint
gases, Templates
Cp = Cv + R
Page 68
34
8/20/2014
Processes
1) Isothermal constant temperature
2) Isochoric constant volume
3) Isobaric constant pressure

4) Adiabatic no exchange of heat
between the system and the
surroundings
Page 69
Thermochemistry
Branch of thermodynamics concerned
with the heat produced or required by
chemical reactions
A reaction vessel and its contents form
a system, and the chemical reactions
result in the exchange of energy
between the system and the
surroundings
Page 70
35
8/20/2014
Calorimetry
Study of heat transfer during physical and
chemical reactions
CALORIMETER device used in calorimetry
to measure energy transferred as heat
thermally isolated / adiabatic
Page 71
Calorimetry
For a calorimeter:
Qcal C cal T
To get heat produced or absorbed:
Q nCT
where Q = heat produced / absorbed
by the reaction
n amount of substance
C - specific heat
T change in temperature;
proportional to Q
Page 72
36
8/20/2014
Calorimetry
Types:
1) Open Type constant pressure;
Qp H
2) Bomb Type constant volume;
Qv U
For reactions:
H is (-) when heat is
produced/exothermic
(+) when heat is
absorbed/endothermic
Page 73
Bond enthalpy
The change in enthalpy required to break
a bond between 2 atoms in an isolated
gaseous molecule, producing dissociated
fragments in the gaseous state
Only applicable to gaseous molecules
having covalent bonds
e.g.: HCl(g) H(g) + Cl(g)
Page 74
37
8/20/2014
Standard enthalpy changes

Change in enthalpy for a process in which the
initial and final substances are in their
standard states
a) ENTHALPIES OF PHYSICAL CHANGE
- changes that do
not cause any
change in the
temperature
- enthalpy of transition
250
200
150
100
50
-50
Page 75
Standard enthalpy changes

b) ENTHALPIES OF CHEMICAL CHANGE
- thermochemical equations or
combinations of chemical reactions
and their corresponding change in
standard enthalpy
e.g.: CH4(g) + O2(g) CO2(g) + H2O(l)
Pure, unmixed
reactants in their
standard states
Pure, separated
products in their
standard states
H= -890 kJ
Page 76
38
8/20/2014
Standard enthalpy /
heat of formation, HF0
- reaction enthalpy for the
formation of a compound from the
elements in their reference states
- T = 298 K; P = 1 bar most stable
state
e.g.: formation of benzene
6C(s,graphite) + 3H2(g) C6H6 (l)
H0f, C6H6 = 49.0 kJ/mol
H0f, elements = 0
Page 77
Standard enthalpy /
heat of reaction, H0rxn
0
H rxn
(nH 0f , products ) (nH 0f ,reac tan ts )
e.g. Calculate the standard reaction

enthalpy of the following:
2HN3 (l) + 2NO(g) H2O2(l) + 4N2(g)
Page 78
39
8/20/2014
Heats of reaction
1) Heat of combustion standard
reaction enthalpy for the
complete oxidation of an organic
compound to CO2 gas and liquid
water (if N is present, also to N2)
e.g.: combustion of glucose
Page 79
Heats of reaction
2) Heat of solution standard reaction
enthalpy when solute is dissolved
in a solvent
3) Heat of neutralization
H+ + OH- H2O
4) Heat of dilution
Page 80
40
8/20/2014
Hesss law of heat summation

The standard enthalpy of an overall
reaction is the sum of the standard
enthalpies of the individual reactions
in which the reaction may be divided
e.g. Calculate the standard enthalpy
of the combustion of propene, C3H6,
given:
Page 81
Temperature dependence of
enthalpy
The standard enthalpies of many
reactions can be computed at different
temperatures using Cp
KIRCHHOFFS LAW:
T2
0
H 0 rxn (T2 ) H rxn
(T1 ) r Cp 0 dT
T1
r Cp 0 (nC p0,m, products ) (nC p0,m,reac tan ts )

Page 82
41
8/20/2014
SPONTANEITY
The natural occurrence of processes
A spontaneous direction of change
does not require work to be done to
bring it about.
> the spontaneous flow of heat is
always unidirectional from the higher
to the lower temperature
All naturally occurring processes always tend to change

spontaneously in a direction which will lead to equilibrium
Page 83
SPONTANEITY
performing a nonspontaneous process
can be possible, but
only if a certain
amount of work is
done
Page 84
42
8/20/2014
The 2nd law of thermodynamics

Recognizes between the spontaneous and nonspontaneous processes
Places a limitation to the 1st law, which does not
have any restrictions on the source of the heat or
direction of its flow
Statements:
1) Clausius Statement
It is impossible for a self-acting machine
unaided by an external agency to move heat
from one body to another at a higher
temperature.
Page 85
The 2nd law of thermodynamics

Statements:
QH
Qc
QH
2) Kelvin-Planck Statement
It is impossible to construct a heat
engine which, while operating in a
cycle, produces no effects except
to do work and exchange heat with
a single reservoir.
3) Kelvin statement
No process is possible in which the
sole result is the absorption of heat
from a reservoir and its complete
QH QC W
conversion into work.
W QH QC
eff
QH
QH
Page 86
43
8/20/2014
The 2nd law of

thermodynamics
Statements:
4) The entropy of an isolated system
never decreases.
Page 87
Entropy, S
Measure of energy dispersed in a
process
A state function; a change in
entropy occurs as a result of a
physical or a chemical change, this
change is at the extent to which
energy is dispersed in a disorderly
manner
Page 88
44
8/20/2014
Entropy, S
The 2nd law statement in terms of entropy:
A spontaneous change is directed towards a
more disorderly dispersal of the total energy
of the isolated system. Stot>0
where Stot - total entropy of the system and
the surroundings
The thermodynamic definition of entropy:
dQrev
T
f dQ
rev
S
i
T
dS
Page 89
Entropy, S
For the surroundings:
dS surr
S
dQsur
Tsur
Qsur
Tsur
For an adiabatic change: Ssur = 0

Clausius Inequality: S >= 0
Page 90
45
8/20/2014
USEFUL EQUATIONS FOR

REVERSIBLE PROCESSES
Page 91
Isothermal mixing of gases

A
pAo, nA
B
pBo, nB
SA
SB
A
pA, nA
B
pB, nB
nA + nB = n T
pA = xApT
pB = xBpT
Page 92
46
8/20/2014
Entropy during phase changes

Phase changes under 1 atm
pressure are reversible
processes
S
H trans
Ttrans
Page 93
Troutons Rule
Many normal liquids have
approximately the same standard
entropy of vaporization which is 85
J/(K-mol).
S
H trans
Ttrans
H trans Ttransx85J /( K mol)

Page 94
47
8/20/2014
Carnot cycle
Cycle a series of operations so
conducted that at the end, the
system is back to its original
state
Named after the French
engineer Sadi Carnot
Consists of 4 stages
Page 95
Carnot cycle
1: reversible isothermal expansion from
A to B at Th
2: reversible adiabatic expansion from B
to C until temperature decreases from
Th to Tc
3: reversible isothermal compression
from C to D until temperature
increases from Tc to Th
4: reversible adiabatic compression from
D to A until temperature increases
from Tc to Th
Page 96
48
8/20/2014
Third Law of Thermodynamics

1. It is impossible to attain the absolute zero
of temperature
2. In an isothermal process involving
condensed pure substances in equilibrium,
the entropy change approaches zero as the
absolute temperature approaches zero and
equals zero when the temperature is zero.
(NERNST HEAT THEOREM)
Page 97
Third Law of
Thermodynamics
3. At absolue zero temperatures, the entropy of
all pure perfect crystalline structures may be
taken to be zero.
*3rd law entropy: entropies reported on the basis
that S0 = 0
- allows for the computation of pure
substances
- S298 K - standard state entropy
Page 98
49
8/20/2014
Third Law of Thermodynamics

Debyes Law - can be used to
calculate for the molar entropy of
substances at temperatures close to
absolute zero
C = bT3
Sm = 1/3(bT3)
Page 99
Absolute Entropies of Liquids

and Gases
The total absolute entropy of a
substance in a particular state at a
given temperature will be the sum
of all the entropy changes that the
substance has to undergo in order
to reach the particular state from
the crystalline solid to absolute zero
Page 100
50
8/20/2014
LIQUIDS
Page 101
Liquids
Liquids have the following properties:
Higher densities than gases
Have definite volume but takes the shape
of the container
Are less compressible than gases
Movement is constant (vibrating) and by
Page 102
modePowerpoint
of slidingTemplates
past one another
51
8/20/2014
Critical phenomena
At critical conditions, the physical properties of
the liquid and vapor become identical, and
there is no distinction between the 2 phases
At the critical point, T=Tc , V=Vc, and P = Pc
At points above and at Tc , the substance
remains as a gas.
If T>Tc , a single phase, denser fluid is present,
known as a supercritical fluid.
*Saturated vapor pressure vapor pressure at
equilibrium of a liquid-gas system
Page 103
Properties of liquids
1) Density ()
Just like for gases, the density of liquids are
affected by pressure and temperature. m
Recall:
V
*Specific gravity the ratio of the density of
a compound / substance to a reference
compound / substance
Reference substances:
For liquids: water at 40C
(=1 g/mL)
For gases: usually air
S.G. =
subs tan ce
ref subs tan ce
Page 104
52
8/20/2014
2) Viscosity ()
- defined as the resistance of a fluid to flow
- in gases, as temperature increases, also
increases
- unit: Poise (P)
1 cP = 0.001 Pa-s
- for liquids, 2 equations can be used:

a) Pouiseuilles equation
b) Stokes Law
Page 105
Ostwald viscometer
Falling sphere viscometer

Page 106
53
8/20/2014
2) Viscosity ()
a) Pouiseuilles equation
used by the Ostwald viscometer
Where P pressure head
r radius of the capillary tube
t time of flow
L length of capillary tube
(absolute viscosity)
V volume of the fluid
Pr 4 t
8LV
Page 107
2) Viscosity ()
a) Pouiseuilles equation used by the
Ostwald viscometer
Using the same viscometers, the
relative viscosities can also be
obtained:
liqd 1 ( t )liqd 1
liqd 2 ( t )liqd 2
Page 108
54
8/20/2014
2) Viscosity ()
b) Stokes Law used by the falling sphere
viscometer
- applicable when the radius of the falling body
is greater than the distance between the
molecules of the fluid
2 r2 ( m )g
9v
(absolute viscosity)
liqd 1 ( m )tliqd 1
liqd 2 ( m )tliqd 2
Where m density of the fluid inside

the cylinder
density of the steel ball
r radius of steel ball
v velocity of the steel ball
Page 109
(relative viscosity)
3) Surface Tension
- the amount of work required to increase the
surface area of the liquid
- as liquid molecules at the surface come into
contact with gas molecules:
> they encounter less attractive forces
since they are surrounded by less liquid
molecules compared to those at the bulk
section
> they are at a higher energy state than
those at the bulk section
Page 110
55
8/20/2014
3) Surface Tension
- as liquid molecules at the surface come into
contact with gas molecules:
> the tendency of the molecules is to
decrease the energy state (to a more
stable state). It forms the shape with
the least surface area that it can assume
for a certain volume: sphere
- the teardrop shape is a spherical drop
affected by gravity
Page 111
3) Surface Tension
- as liquid molecules at the surface come
into contact with solid surfaces:
* cohesion the interaction of liquid
molecules with one another
* adhesion the interaction of liquid
molecules with solid molecules
- The relative strengths of these 2
dictate the shape of the surface
(meniscus)
Page 112
56
8/20/2014
3) Surface Tension
- as liquid molecules at the
surface come into contact with
solid surfaces:
Page 113
3) Surface Tension
- 2 methods of measuring surface
tension:
a) capillary rise method
h gr
2
Where h - height
density
g - gravity
r radius of the capillary
tube
Page 114
57
8/20/2014
3) Surface Tension
- 2 methods of measuring
surface tension:
b) De Nuoy ring method /
tensiometer
Where m weights used to restore
the tensiometers horizontal
position
L mean circumference of the
ring
correction factor
mg
2L
Page 115
EQUILIBRIUM
A condition of maximum stability appropriate
with the state of each system
All changes in nature tend to go towards
equilibrium
WORK results when the tendencies of systems
to reach equilibrium are harnessed in some
way; therefore NO WORK can be harnessed
from a system in equilibrium
Page 116
58
8/20/2014
EQUILIBRIUM
For Reversible processes:
Maximum work is obtained
For Irreversible processes: work
is always less than the maximum;
the difference is yielded as heat
Page 117
Free energies
Energies produced as the system
approaches equilibrium
Helmholtz Free Energy, A
A U TS
Since U and S are state functions,
A U T S
Under isothermal and reversible conditions,
Q T S
Therefore
A Wmax
maximum work function
Page 118
59
8/20/2014
Free energies
Gibbs Free Energy, G
G H TS
Since H and S are state functions, under

isothermal and reversible conditions,
G H T S
or
G A PV
G Wmax add
Maximum additional nonexpansion work
Page 119
Free energies
Gibbs Free Energy, G
From the Helmholtz free energy, the maximum
work is quantified, but a part of this work will
be used for mechanical / P-V work against the
atmosphere (W=PV), therefore G can also
be expressed as:
net energy G Wmax PV

Where net energy is the available energy
after doing mechanical work, or the
maximum net energy at constant nonexpansion work
Page 120
60
8/20/2014
Standard Gibbs energy of

reaction
Gr H r T Sr
Gr nG f , pdts nG f ,react
3 possible conditions for free

energy change:
A+B C+D
G=
A+B C+D
G=
A + B C + D
G=
Page 121
Calculation of Gibbs energy of

reaction
At constant temperature
dG VdP
Since for gases, V = nRT/P,
nRTdP
P
P
G nRT ln 2
P1
dG
For solids and liquids

G V ( P2 P1 )
Page 122
61
8/20/2014
REFERENCES
http://www.chem.purdue.edu/gchelp/liquids/
vpress.html
http://chemed.chem.wisc.edu/chempaths/Ge
nChem-Textbook/Bond-Enthalpies-718.html
Page 123
62

Physical chemistry lecture on gases and thermodynamics

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Physical chemistry lecture on gases and thermodynamics

Uploaded by

Copyright:

Available Formats

8/20/2014

ChE Course Integration 1 Review

Sherrie Mae S. Medez

The Perfect / ideal gas

The ideal gas law

The ideal gas law

The ideal gas law variables

Force (can also be weight)

- the force comes from the ceaseless motion

The ideal gas law variables

Force (can also be weight)

- units: atm, Torr, bar, mmHg, Pascal, psi

The ideal gas law variables

wall will continue to move until Pleft =

- when movable wall stops moving, then

The ideal gas law variables

The ideal gas law variables

Physical Illustration of temperature:

- if no change is observed, then there is an

The ideal gas law variables

*When the diathermic wall stops transferring

The ideal gas law variables

If A is in thermal equilibrium with B,

-This law allows for the consideration of temperature

The gas laws

3) Alternative to Charles Law

The gas laws

The gas laws

- gases obey this at low pressure and high temperature

The gas laws

Mixtures of ideal gases

Mixtures of ideal gases

where pT = total pressure

Mixtures of ideal gases

for a mixture xA xB xc ... 1.0

the pressure that will be

Mixtures of ideal gases

Obtained from the experiment:

Mixtures of ideal gases

Mixtures of ideal gases

Variation of atmospheric pressure

Kinetic molecular theory

Kinetic molecular theory

Kinetic molecular theory

Kinetic molecular theory

6) At relatively low pressures, the average

Kinetic molecular theory

Speeds of gas molecules

Root mean squared speed, Vrms

*In reality, speeds of molecules span over a wide range ,

Mean Free Path

Kinetic energy of translation

Van der waals equation of state

Where Tc and Pc,

OTHER EQUATIONS OF STATE

PVm A BP CP2 DP3 .....

where A, B, C, and D are virial coefficients

OTHER EQUATIONS OF STATE

OTHER EQUATIONS OF STATE

Where B, C, . Are virial coefficients

Saturated Vapor Pressure: established at

substituting into the VDW equation of

Thermodynamics can be used for: