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8/20/2014

Physical Chemistry
Lecture no. 1

ChE Course Integration 1 Review

Sherrie Mae S. Medez

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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
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OUTLINE

LIQUIDS
characteristics
physical properties
SAMPLE PROBLEMS

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GASES

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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
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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
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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)

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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)

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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

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The ideal gas law variables


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

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The ideal gas law variables


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
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The ideal gas law variables


1) PRESSURE
* Manometer used to measure
the pressure of a gas inside a
container

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Source: http://www.efunda.com/formulae/fluids/images/Manometer_A.gif

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The ideal gas law variables


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
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conducting rigid wall

The ideal gas law variables


2) TEMPERATURE

*When the diathermic wall stops transferring


heat, then THERMAL EQUILIBRIUM (equality
of temperature) is achieved
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The ideal gas law variables


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)
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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
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The gas laws

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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
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The gas laws

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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

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Mixtures of ideal gases


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

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Mixtures of ideal gases


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


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Mixtures of ideal gases


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

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Mixtures of ideal gases


GRAHAMS LAW
d g1
dg 2

uavg1
uavg 2

MWg 2
MWg1

Obtained from the experiment:


NH3(g) + HCl(g) NH4Cl(s)

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Mixtures of ideal gases


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
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Mixtures of ideal gases


AMAGATS LAW OF COMBINING
VOLUMES

vf
v ft
for gases,

vi
vm

vm

v fi xi

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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

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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

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Kinetic molecular theory


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.
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Kinetic molecular theory


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.
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Kinetic molecular theory


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.
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Kinetic molecular theory


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.
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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 ,


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given by the MAXWELL
SPEED
DISTRIBUTIONS.

Maxwell speed
distrIbutions

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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

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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
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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

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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
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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
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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

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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
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OTHER EQUATIONS OF STATE


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
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Rc Bo
T2
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OTHER EQUATIONS OF STATE


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
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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

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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
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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.

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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

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THERMODYNAMICS

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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

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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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.

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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

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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)
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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

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WORK
Defined as mechanical or P-V work
The transfer of energy that makes use
of organized motion

Source: Physical
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Chemistry
Templates
8th ed by Atkins

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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

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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

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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

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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
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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
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Calorimetry
Study of heat transfer during physical and
chemical reactions
CALORIMETER device used in calorimetry
to measure energy transferred as heat
thermally isolated / adiabatic

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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
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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
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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)
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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

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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

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H= -890 kJ

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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
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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)
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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

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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

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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:
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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 )


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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
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SPONTANEITY
performing a nonspontaneous process
can be possible, but
only if a certain
amount of work is
done

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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.
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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
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The 2nd law of


thermodynamics
Statements:
4) The entropy of an isolated system
never decreases.

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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
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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
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dS

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Entropy, S
For the surroundings:
dS surr
S

dQsur
Tsur

Qsur
Tsur

For an adiabatic change: Ssur = 0


Clausius Inequality: S >= 0
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USEFUL EQUATIONS FOR


REVERSIBLE PROCESSES

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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

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Entropy during phase changes


Phase changes under 1 atm
pressure are reversible
processes
S

H trans
Ttrans

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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)


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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

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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
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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)

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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
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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)
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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

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LIQUIDS

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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
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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
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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
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S.G. =

subs tan ce
ref subs tan ce

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Properties of liquids
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
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Properties of liquids

Ostwald viscometer

Falling sphere viscometer


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Properties of liquids
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

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Properties of liquids
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
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Properties of liquids
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

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(relative viscosity)

Properties of liquids
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
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Properties of liquids
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
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Properties of liquids
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)
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Properties of liquids
3) Surface Tension
- as liquid molecules at the
surface come into contact with
solid surfaces:

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Properties of liquids
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

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Properties of liquids
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

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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
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EQUILIBRIUM
For Reversible processes:
Maximum work is obtained
For Irreversible processes: work
is always less than the maximum;
the difference is yielded as heat

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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

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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

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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
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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

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G=
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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


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G V ( P2 P1 )
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REFERENCES
http://www.chem.purdue.edu/gchelp/liquids/
vpress.html
http://chemed.chem.wisc.edu/chempaths/Ge
nChem-Textbook/Bond-Enthalpies-718.html

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