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CHAPTER 5.

0
STATES OF MATTER

5.1 Gas
5.2 Liquid
5.3 Solid
At the end of the lesson, student should be able to :

(a) Explain the general properties of gas in terms of arrangement of

particle, density and compressibility.


(b) Explain qualitatively the basic assumptions of the kinetic
molecular theory of gases for an ideal gas.
(c) Define gas laws
(i) Boyles Law
(ii) Charless Law
(iii) Avogadros Law
(d) Sketch and interpret the graphs of Boyles and Charless laws
(e) Perform calculations involving gas laws.
(f) derive ideal gas equation based on the gas laws
(g) perform calculations using the ideal gas equation
(h) determine the molar mass and density of a gas using ideal gas
equation
(i) Define:

Partial pressure

Dalton's law
(j) perform calculation using Dalton's law
(k) compare the ideal and non-ideal behaviours of gases in terms of
intermolecular forces and molecular volume
(l) explain the conditions at which real gases approach
the ideal behaviour.
(m) explain qualitatively van der Waals equation and relate the
values of a and b to intermolecular forces and molecular volume
of a gas
General
Properties
of Gas

Particles of gas are far apart and fill the available space.

Gases assume the volume and shape of their containers.

can be compressed due to the particles being


so small and are relatively far apart from one another.

Gases have relatively low densities.


Kinetic Molecular Theory of
Gases

Describes the behavior of an ideal gas

Ideal gas : gases which obey the ideal gas


equation (PV = nRT)
The theory is based on the following assumptions:
1) Gas molecules are very tiny that their size are negligible
compared to the volume of the container.
(having mass but no volume)
2) Gas molecules move in straight lines and are at
a constant motion unless they collide.
3) Molecular collisions are elastic no energy is lost during
collisions.
4) Attractive and repulsive forces between gas particles are
negligible.
5) The average kinetic energy of the particles is proportional
to the absolute temperature.
The Gas Laws
a) Boyles Law :
The volume of fixed amount of gas at constant
temperature is inversely proportional to the gas
pressure

V 1 (no of mole and temperature are constant)


P

PV = k Where:
k = constant
V = volume
P = pressure
T = temperature
n = number of moles
at different pressure and volume :

P1 V1 = P2 V2
Where
P1 = initial pressure
V1 = initial volume
P2 = final pressure
V2 = final volume
G ra p h o f P v e rs u s V G ra p h o f P v e rs u s 1
V
P
P

1
V V
pressure is inversely pressure is directly
proportional to volume proportional to 1
volume
Graph of PV versus P

PV

PV = constant

P
Example 1

A sample of chlorine gas occupies a volume of 2 L at a pressure


of 1 atm. Calculate the pressure of the gas if the volume is
increased to 5 L at constant temperature.

0.4 atm
Example 2

The pressure of a sample of hydrogen gas in a 50.0 mL container is


765 mmHg. The sample is then transferred into another container and
the measured pressure is 825 mmHg. What is the volume of the second
container?

46.36 mL
a) Charless Law :
The volume of a fixed amount of gas at
constant pressure is directly proportional to the
absolute temperature of the gas (in Kelvin).

V T (no of mole and pressure


constant)
V
=k Where :
T
k = constant
T = absolute temper
V = volume
At different volume and temperature:

T = absolute temperature
in Kelvin (K)
V1 V2

T1 T2 T(K) = TC + 273.15

Where V1 = initial volume


T1 = initial temperature
V2 = final volume
T2 = final temperature
Graph of volume versus temperature :

V V

0 T(K) -273.15
T(0C)
Example 1

A sample of carbon monoxide gas occupies 3.2 L


At 125 C. The sample is then cooled at constant
pressure until it contracts to 1.54 L. Calculate the
final temperature in degree Celsius.

-81.54 C
Example 2

A sample of gas trapped in a capillary tube by a


plug of mercury at 22 oC has a volume of 4.5
mL.
Calculate the volume of the gas when the
capillary
tube is heated to 60 oC.

5.08 mL
The Combination of Boyles and Charless Law
1
Boyles law : V
P
Charless law : VT
T
V
P
T
V =k
P
PV
=k
T

P1V1 =
P2 V2
T1 T2
Example 1

A sample of methane gas occupies 25.5 L at


298.15 K and 153.3 kPa. Find its volume at STP.

Ans : 35.32 L
Example 2
2 moles of chlorine gas kept in a cylinder
with piston occupies a volume of 49 L.
When another 3 moles of chlorine gas is
pumped into the cylinder at constant
temperature and pressure the piston
moves upwards to accommodate the gas.
Calculate the final volume of the gas.
Ans : 73.5 L
C) Avogadros Law
At constant pressure and temperature,
temperature the volume of a
gas is directly proportional to the number of moles of the
gas present
V n (P and T are constant)
V = k n
V
=k
n where :
n = number of moles
V1 V2 k= constant

n1 n2
Combination of Boyle's law, Charles's law and Avogadro's law :
1
B o y l e 's L a w : V
P
C h a rle s ' L a w : V T
A v o g a d r o 's L a w : V n

nT
V Where :
P
R = gas constant
V = R
nT
T = Temperature(K)
P
n = number of moles
PV = nRT V = volume
Ideal gas equation P = Pressure
Value of R depend on the unit of pressure and
volume used in the equation.
unit of unit of value of unit of R
pressure volume R
atm L or dm3 0.08206 L atm mol1 K1

Nm2 m3 8.314 Nm mol1 K1


or J mol1 K1
Pa
Example 1

A steel gas tank has a volume of 275 L and is filled


with 0.485 kg of O2. Calculate the pressure of O2 if
the temperature is 29 oC.

Ans : 1.36 atm


Example 2

A sample of chlorine gas is kept in a 5.0 L container


at 228 torr and 27 C. How many moles of gas are
present in the sample?

Ans : 0.06 mol


MOLAR MASS and DENSITY
CALCULATION
Molar mass and density of a gas can be
calculated
by rearranging the Ideal Gas Equation:
P V nR T

m m
PV = R T w h e re : n =
M r M r

m R T Mr = molar mass of a gas


M r=
PV
D e n s ity o f a g a s
P V nR T
m
PV= RT
M r
mRT
P =
VM r
dR T w h e re ,
P =
M r d = d e n s ity o f a
gas
PM r
d =
RT
Example
1
Calculate the density of ammonia (NH3) in
grams per litre (g/L) at 752 mmHg and 55 C.

Ans : 0.625 gL-1


Example 2

A chemist has synthesized a greenish-yellow compound of


chlorine and oxygen and finds that its density is 7.71 g L-1 at
36 C and 2.88 atm. Calculate the molar mass of the
compound.

Ans : 67.9 gmol-1


Example 3

W h a t m a s s o f K C lO 3 is r e q u ir e d to p r o d u c e
2 .4 0 L O 2 g a s th a t m e a s u r e d a t a p r e s s u r e o f
1 a tm a n d a te m p e ra tu re o f 2 6 o C . T h e
r e a c tio n e q u a tio n is
2 K C l O 3 ( s ) 2 K C l ( s ) + 3 O 2 ( g )
Daltons Law of Partial Pressure
The total pressure of mixture of non reacting gases is the
sum of the partial pressures exerted by each of the gas in the
mixture

(Partial pressure is the pressure of individual gas component in a


mixture).

- For a mixture of 3 gases, A,B and C :

PT = P A + P B + P C
A c c o r d in g to id e a l g a s e q u a tio n :
nART
p re s s u re e x e rte d b y g a s A = P A =
V
nBR T
p re s s u re e x e rte d b y g a s B = P B =
V
in th e m ix tu r e o f g a s e s A a n d B :
P T = P A + P B
nART nBR T
=
V V
= (n A + n B )R T n TR T
V P T =
V
w hen nA + nB = nT
M o le fr a c tio n a n d p r e s s u r e s
D a lt o n s t h e o r y a llo w s u s t o f o r m a r e la t io n s h ip
b e t w e e n M o le f r a c t io n s , p a r t ia l p r e s s u r e a n d a to t a l
p re s s u re .
C o n s id e r th e fo llo w in g c o n d itio n a t c o n s ta n t T
and V
If P n RT A A
P to ta l n to ta l( R T )
Thus: PA n A (R T ) PA n
A
P to ta l n to ta l ( R T ) P T o ta l n T o ta l

P A X A P to ta l X A = m o le fr a c tio n o f g a s A
Example
1
A gaseous mixture of 7.00 g N2 and 3.21 g CH4 is placed in a
12.0 L cylinder at 25 oC.

a) What is the partial pressure of each gas?


b) What is the total pressure in the cylinder?
Ans :a) 0.501 atm , 0.41 atm
b) 0.92atm
Example 2

A mixture of gases contains 4.53 moles of neon, 0.82 moles


of argon and 2.25 moles of xenon. Calculate the partial
pressure of the gases if the total pressure is 2.15 atm at a
certain temperature.

Ans : P Ne = 1.28 atm,, P Ar = 0.079 atm, P Xe = 0.63 atm,


Example
3
A sample of gas at 5.88 atm contains 1.2 g CH4, 0.4 g H2 and
0.1 g He. Calculate :

a) The partial pressure of CH4, H2 and He in the mixture.


b) What is the partial pressure of CH4 and H2 if He is removed?

Ans : a) P CH4= 1.74 atm,P H2 = 3.92 atm, P He= 0.49 atm


b) P CH4= 1.6 atm,P H2 = 4.28 atm
One of the applications of Daltons Law is to calculate the pressure
of a gas collected over water ( for gases that not soluble in water).

gas gas + water vapour

The gas collected is actually a mixture of the gas and water vapour.

PT Pgas PH 2O
Vapour pressure of water, Pwater = 23.8 torr
Example 1

Consider the reaction below :

2KClO3 2KCl + 3O2


A sample of 5.45 L of oxygen is collected over water at a total
pressure of 735.5 torr at 25 C. How many grams of oxygen have
been collected?
(at 25C, Pwater = 23.8 torr)
Ans : 7.011 g
Example 2

Excess amount of hydrochloric acid is added to 2.5 g of pure


zinc. The gas produced is collected over water in a gas cylinder
at 28 oC and 100.0 kNm-2. Calculate :

a) the number of mole of gas produced in the reaction.


b) the volume of gas collected in the cylinder.
Ans : a) 0.038 mol
b) 0.95 L
Ideal gas
any gas that obeys the ideal gas
equation and has the properties as
outlined by the Kinetic Molecular
Theory
Deviation from Ideal Behavior
real gas (non-ideal gas) : gases which do not obey
ideal gas properties
Real gases do not behave ideally because:
i) gas molecules do have its own volume and they occupy
some space.
ii) gas molecules do have intermolecular forces acting
between them
R e a l g a s e s b e h a v e a lm o s t id e a lly a t a
lo w p r e s s u r e a n d h ig h te m p e r a tu r e .
R eason:
A t lo w p r e s s u r e :
T o a c h ie v e a lo w p r e s s u r e , th e v o lu m e o f
a c o n ta in e r is in c r e a s e d .
T h u s , th e m o le c u le s w ill b e fa r a p a r t fr o m
a n o th e r , h e n c e th e in te r m o le c u la r fo r c e s
c a n b e n e g le c te d .
A t a lo w p r e s s u r e th e s iz e o f a c o n ta in e r is
e x tr e m e ly la r g e c o m p a r e d to th e s iz e o f
m o le c u le s , th u s th e s iz e o f m o le c u le s c a n
b e n e g le c te d .
Reason :
At low pressure
At low pressure, the volume of a
container is very large
Thus the molecules will be more far
apart from one another. Hence the
intermolecular forces can be
neglected.
At low pressure, the volume of the
container is extremely large compared
to the size of the molecules, thus the
volume can be neglected
A t h ig h te m p e r a tu r e

T h e g a s m o le c u le s h a v e h ig h k in e tic
e n e r g ie s a n d m o v e a t h ig h s p e e d

T h e m o le c u le s a r e a b le to fr e e th e m s e lv e s
fr o m th e in te r m o le c u la r fo r c e s th a t a c t
b e tw e e n th e m .

T h e in te r m o le c u la r fo r c e s c a n b e
n e g le c te d , th u s th e y b e h a v e a lm o s t
id e a lly .
G r a p h P V /R T a g a in s t P fo r N 2
a t d iffe r e n t te m p e r a tu r e s
PV
RT 273K
T h e lin e s
a p p ro a c h th e
600K id e a l lin e w h e n
1000K T in c r e a s e s

T h e v a lu e a p p r o a c h e s 1 .0
a t a v e r y lo w p r e s s u r e

9
Van der Waals Equation
Since real gas does not exhibit ideal gas behavior
at high pressure and low temperature :
the ideal gas equation (PV=nRT) needs to be
adjusted
adjusting the equation, two parameters need to
be reconsidered :
attractive forces between the gas molecules
volume of the gas molecules
a) Attractive Forces Between Molecules

Attractive forces which act between the gas molecules will :

make the molecules move slower

give less impact to the wall

pressure exerted by the real gas is less compared to the ideal


gas
since Preal < Pideal
2

the term pressure need to be corrected by adding coefficient a


n
V2

n = n u m b e r o f m o le s

P = P + n 2a a = c o rre c tin g fa c to r fo r
id e a l re a l p re s s u re
V2 V = v o lu m e o f c o n ta in e r
(b ) V o lu m e o f th e g a s m o le c u le s

S in c e th e g a s o c c u p y a s iz e a b le p o r tio n
o f a c o n ta in e r , th e s p a c e in w h ic h th e
m o le c u le s a r e a b le to m o v e a r e le s s
th a n th e v o lu m e o f th e c o n ta in e r .
V r e a l < V c o n ta in e r
T h e c o r r e c tio n fa c to r d o n e to th e
v o lu m e is :
nb v

V = v o lu m e

V = V c o n ta in e r - nb n = n u m b e r o f m o le s
b = s iz e fa c to r
R e f e r r in g t o t h e id e a l g a s e q u a t io n :

PV = nRT

B y r e p la c in g th e s e in to th e e q u a tio n

P id e a l = P re a l + n 2a & V = V c o n ta in e r - nb
V2

(P re a l + n 2a ) ( V n b ) = n R T
V2

T h e v a n d e r W a a ls e q u a tio n
V a lu e o f a :

a is a p o s itiv e c o n s ta n t w h ic h d e p e n d s o n th e
s tre n g th o f th e a ttra c tiv e fo rc e s b e tw e e n m o le c u le s
M o le c u le s w ith a h ig h e r v a lu e o f a h a v e s tro n g e r
a ttra c tiv e fo rc e s .

V a lu e o f b :
b is a c o n s ta n t to re p re s e n t th e v o lu m e o c c u p ie d
b y th e m o le c u le s .

L a rg e r m o le c u le s h a v e b ig g e r v a lu e o f b
5.2 Liquids
At the end of this topic, students should
be able to :

a) Explain the properties of liquids : shape,


volume, surface tension, viscosity, compressibility
and diffusion.
b)Explain vaporization process and condensation
process based on kinetic molecular theory and
intermolecular forces.
c) Define vapour pressure and boiling point
d) Relate :
- intermolecular forces to vapour pressure
- vapour pressure to boiling point
The properties of Liquids
1. Volume and Shape
has a definite volume but not a definite shape
the particles are arranged closely but not rigidly
held together by a strong intermolecular forces
but not strong enough to hold the particles
firmly in place
particles are able to move freely
thus, a liquid flows to fit the shape of its container
and is confined to a certain volume
2. Surface tension
Surface tension is the amount of energy
required to stretch or increase the surface of
a liquid by a unit area
Surface tension is caused by the attractive
forces and the direction of the force acting
between
molecules
Molecules within a liquid experienced
intermolecular attractive forces in all
directions by their neighbouring molecules
however, molecules at the surface are pulled
inwards and sideways from the neighbouring
molecules
F ig . 1 1 .8

m o le c u le a t
th e s u rfa c e

m o le c u le w ith in
th e liq u id
these intermolecular attractive forces will
pull the molecules into the liquid
Thus, cause the surface to stretch and
tighten
the stronger the intermolecular attractive
forces, the higher the surface tension
3. Viscosity
is a measure of the resistance of a liquid
to flow

the greater the viscosity,


viscosity the more slowly
the liquid flows.

Viscosity may be explained in terms of the


intermolecular forces present in a liquid
The factors affecting the viscosity :
i) The strength of intermolecular forces
Liquids that have strong intermolecular forces have
higher viscosity

ii) The size of the molecules


Liquids with larger size (higher molar mass)
is more viscous because it has stronger
intermolecular forces
iii) The temperature of the liquid
At higher temperature, molecules have
higher
kinetic energy,
the molecules move faster
molecules can overcome the intermolecular
attractive forces more easily
resistance to flow decrease
Viscosity decrease
4. Compressibility
in liquid, the particles are packed closely
together
thus, there is very little empty space
between the molecules
liquids are much more difficult to
compress than gas
5. Diffusion
Diffusion is the movement of liquid from one
fluid through another.
Diffusion can occur in a liquid because molecules
are not tightly packed and can move randomly
around one another.
Vaporisation Process
a process in which molecules escape from
liquid into gaseous state through a surface
molecules in a liquid moves freely, collide

with each other and posses different


magnitudes of kinetic energy
when the kinetic energy is sufficient
enough to overcome the intermolecular
forces acting on them, the molecules will
escape as vapour.
Factors affecting the rate of vaporization :
i) Surface area
~ the surface area , the chances for the
molecules to escape from the surface
surface area , evaporation rate
ii) Temperature
~ temperature , the kinetic energy
more molecules have enough energy to
overcome the attractive intermolecular forces
and escape from the surface of the liquid
~ thus evaporation rate
Condensation Process
a process whereby gaseous molecules turn to liquid
some of the vapour molecules may lose their kinetic
energy during the collision
they do not have enough energy to remain as vapour
molecules
they reached the surface of the liquid and trapped
by the attractive forces
if they cannot overcome the attractive forces,
these vapour molecules return as liquid molecules
the process is known as condensation
V apour Pressure

m o le c u l e s e s c a p e f r o m t h e s u r f a c e o f a l iq u id
: r e f e r r e d a s v a p o u r m o le c u le s
P r e s s u r e e x e r t e d b y t h e v a p o u r m o le c u le s
o n t h e s u r f a c e o f a l iq u id is k n o w n a s t h e
vapour pressure

I f e v a p o r a t io n o c c u r s in a n o p e n c o n t a in e r ,
v a p o u r m o le c u le s w ill d if f u s e d a w a y u n t il
t h e liq u id d r ie s u p
in a c lo s e d s y s t e m :
v a p o u r m o le c u le s w h ic h le a v e s t h e s u r f a c e a r e
t r a p p e d in t h e c lo s e c o n t a in e r
t h e s e v a p o u r m o le c u le s a r e in c o n s t a n t r a n d o m
m o t io n
t h e m o le c u le s s t r ik e t h e w a ll o f c o n t a in e r a n d
ex ert som e pressure
A s t h e q u a n t it y o f m o le c u le s in t h e v a p o u r p h a s e
in c r e a s e , s o m e m o le c u le s m a y lo s e e n e r g y a n d
condense
E v e n t u a lly ,
t h e r a t e o f e v a p o r a t io n = t h e r a t e o f c o n d e n s a t io n .
( T h e s y s t e m a c h ie v e d d y n a m ic e q u ilib r iu m )
A t e q u ilib r iu m , t h e n u m b e r o f v a p o u r m o le c u le s
a b o v e liq u id a r e c o n s t a n t .
F actor that affects the vapour pressure
T em perature

A p p ly in g t h e h e a t c a u s e s m o r e m o le c u le s h a v e h ig h
k in e t ic e n e r g y
M o r e m o le c u le s w ill b e a b le t o o v e r c o m e t h e
in t e r m o le c u la r f o r c e s a n d e s c a p e f r o m t h e liq u id t o
form vapour
T em perature , vapour pressure

I n t e r m o le c u la r f o r c e s

M o le c u le s w it h w e a k in t e r m o le c u la r f o r c e s c a n e a s ily
v a p o u r is e d
M o r e v a p o u r m o le c u le s w ill e x e r t p r e s s u r e o n t h e liq u id
surface
I n t e r m o le c u la r f o r c e s , v a p o u r p r e s s u r e
B o ilin g

A p r o c e s s in w h ic h liq u id m o le c u le s
c h a n g e to v a p o u r a t a p a r tic u la r
te m p e r a tu r e a n d a t a n a tm o s p h e r ic
p re s s u re .
H a p p e n s th r o u g h o u t th e liq u id .
E v a p o r a tio n
liq u id m o le c u le s c h a n g e to v a p o u r a t
a n y te m p e ra tu re a n d p re s s u re .
O c c u r s o n ly a t th e s u r fa c e o f a liq u id
B o ilin g P o in t: th e te m p e ra tu re a t
w h ic h t h e v a p o u r p r e s s u r e o f a l i q u id i s
e q u a l to th e e x t e r n a l a t m o s p h e r ic
p re s s u re .

N o rm a l B o ilin g P o in t: th e te m p e ra tu r e
a t w h ic h a liq u id b o ils w h e n t h e e x t e r n a l
p re s s u re is 1 a tm ( t h a t is t h e v a p o u r
p re s s u re is 7 6 0 m m H g )
B o ilin g P o in t - p r o c e s s
I n c r e a s in g t h e t e m p e r a t u r e w ill in c r e a s e in t h e v a p o u r
pressure.

A s h e a t is a p p lie d , t h e v a p o u r p r e s s u r e o f a s y s t e m w ill
in c r e a s e u n t il it r e a c h e s a p o in t w h e r e b y t h e v a p o u r
p r e s s u r e o f t h e liq u id s y s t e m is e q u a l t o t h e
a t m o s p h e r ic p r e s s u r e .

B o ilin g o c c u r s a n d t h e t e m p e r a t u r e t a k e n a t t h is p o in t
is k n o w n a s t h e b o ilin g p o in t .

A t t h is p o in t , t h e c h a n g e o f s t a t e f r o m liq u id t o g a s
o c c u r s n o t o n ly a t t h e s u r f a c e o f t h e liq u id b u t a ls o in
t h e in n e r p a r t o f t h e liq u id .

B u b b le s f o r m w it h in t h e liq u id .
F a c to r s a ffe c tin g th e b o ilin g p o in t:

1 . A tm o s p h e r ic p r e s s u r e
W h e n t h e e x t e r n a l a t m o s p h e r ic p r e s s u r e is
lo w , liq u id w ill b o il a t a lo w e r t e m p e r a t u r e

2 . In t e r m o le c u la r f o r c e s
A s u b s t a n c e w it h w e a k in t e r m o le c u l a r f o r c e s
c a n e a s i l y v a p o u r is e a n d t h e s y s t e m r e q u ir e s
le s s h e a t t o a c h ie v e a t m o s p h e r ic p r e s s u r e ,
t h u s it b o ils a t a lo w e r t e m p e r a t u r e .
5.3 Solid
O BJECTIVE
( a ) S t a t e t h e p r o p e r t ie s o f s o lid .
( b ) E x p la in t h e p r o c e s s o f :
- f r e e z in g - s u b lim a t io n
- m e lt in g - d e p o s it io n
( c ) D if f e r e n t ia t e b e t w e e n a m o r p h o u s a n d c r y s t a llin e
s o lid s .
( d ) D e s c r ib e t h e t y p e s o f b o n d in g a n d t h e
in t e r p a r t ic le / in t e r m o le c u la r f o r c e s in v o lv e d in t h e
f o llo w in g c r y s t a llin e s o lid s u s in g a p p r o p r ia t e e x a m p le s .
i. m e t a llic iii. m o le c u la r c o v a le n t
ii. io n ic iv . g ia n t c o v a le n t
Properties of solid

1.Particles are closely arranged and regularly in


order
2. Rigid arrangement- particles can vibrate,
rotate about fixed position and cannot move
freely without disrupting the whole structure.
3. Has definite shape and volume.
4.Has strong forces between the particles.
5. Has high densities.
6. Incompressible.
7.Diffusion within the solid is extremely slow.
In p r in c ip le , s o lid , liq u id a n d g a s s t a t e s a r e
in t e r c o n v e r t ib le

liq u id

s u b lim a tio n

d e p o s itio n
s o lid gas 5
M e l t in g ( F u s io n ) P r o c e s s
S o lid is c h a n g in g in t o a liq u id
W h e n a s o lid s u b s t a n c e is h e a t e d :
- it s p a r t ic le s g a in e n e r g y
- t h e r e f o r e a b le t o v ib r a t e m o r e r a p id ly
- a t c e r t a in t e m p e r a t u r e , t h e k in e t ic e n e r g y is h ig h e r
e n o u g h t o o v e r c o m e t h e in t e r m o le c u la r f o r c e s o f
a t t r a c t io n b e t w e e n s o lid p a r t ic le s .
t h e p a r t ic le s a r e f r e e t o m o v e a n d t h e s o lid s t a r t t o
m e lt
M e lt in g p o in t t h e t e m p e r a t u r e a t w h ic h s o lid a n d
liq u id c o e x is t in e q u ilib r iu m
F r e e z in g ( S o l id ifi c a t io n ) P r o c e s s

L iq u id is c h a n g in g in t o a s o lid
w h e n t h e t e m p e r a t u r e o f a liq u id is lo w e r e d , t h e
k in e t ic e n e r g y o f t h e liq u id p a r t ic le s d e c r e a s e s
t h e liq u id p a r t ic le s v ib r a t e a t a s lo w e r ra t e
w h e n t h e in t e r m o le c u la r f o r c e s a r e s t r o n g
e n o u g h t o h o ld t h e p a r t ic le s t o g e t h e r in a fi x e d
a n d o r d e r ly a rr a n g e m e n t , t h e liq u id f r e e z e s .

F r e e z in g p o in t a t e m p e r a t u r e a t w h ic h t h e liq u id a n d
s o lid p h a s e s o f a s u b s t a n c e s c o e x is t a t e q u ilib r iu m .
S u b l im a t io n P r o c e s s
Th e p r o c e s s b y w h ic h a s u b s t a n c e c h a n g e s
d ir e c t ly f r o m s o lid t o t h e g a s e o u s s t a t e w it h o u t
p a s s in g t h r o u g h t h e liq u id s t a t e .
O c c u r s o n s o lid w it h w e a k in t e r m o le c u la r f o r c e s
o f a t t r a c t io n

D e p o s it io n P r o c e s s
Th e p r o c e s s w h e r e m o le c u le s f r o m v a p o u r s t a t e
c h a n g e t o t h e s o lid s t a t e .
Th e o p p o s it e p r o c e s s o f s u b lim a t io n
T y p e s o f S o l id

c r y s t a l l in e s o l id a m o r p h o u s s o l id
A s o lid t h a t h a s h ig h ly o rd e r e d S o lid t h a t d o e s n o t h a v e a
s t r u c t u r e w h e re a t o m s , io n s o r re g u la r t h r e e d im e n s io n a l
m o le c u le s s h o w a r e g u la r a rr a n g e m e n t o f a t o m s o r
re p e t it io n in t h re e d im e n s io n a l m o le c u le s
a rra n g e m e n t F o rm e d w h e n a sa t u ra t e d
F o rm e d w h e n a s a t u ra t e d liq u id is c o o le d r a p id ly
liq u id is c o o le d s lo w ly E x a m p le :
It s a t o m s , m o le c u le s o r io n s g la s s
o c c u p y s p e c ifi c p o s it io n p la s t ic m a t e r ia l
E x a m p le : ic e , s u g a r, s a lt
c h a rc o a l
T y p e s o f C r y s t a l l in e S o l id

1 . M e t a llic s o lid
C lo s e p a c k e d s t ru c t u re
C o m p o se d o f a to m s o f th e sa m e m e t a l lin k e d
t o g e t h e r b y m e t a llic b o n d
T h e p ro p e rt ie s o f m e t a l:
H ig h e le c t ric a l a n d t h e rm a l c o n d u c t iv it y
L u s t re
D u c t ile a n d m a lle a b le
E x a m p le s : a ll m e t a llic e le m e n t s : N a , M g , F e
2. I o n ic s o lid s
c o n s is t o f io n s ( c a t io n & a n io n ) h e ld t o g e t h e r b y io n ic
bonds
P h y s ic a l p r o p e r t ie s o f io n ic s o lid :
- H ig h m e lt in g p o in t
- H a r d b u t b r it t le
- D o e s n o t c o n d u c t e le c t r ic it y in t h e s o lid s t a t e b u t
d o e s c o n d u c t e le c t r ic it y in m o lt e n s t a t e o r in
aqueous state.
E x a m p le : N a C l, C s C l
3 . M o le c u la r c o v a le n t s o lid
c o m p o s e d o f m o le c u le s h e ld t o g e t h e r b y
in t e r m o le c u la r fo rc e s (v a n der W a a ls
a n d / o r h y d ro g e n b o n d s)
E x a m p le : io d in e [ I 2 (s) ]
4. G ia n t c o v a le n t s o lid s
v e r y la r g e m o le c u le s / g ig a n t ic s t r u c t u r e
c o m p o se d o f a t o m s lin k e d to g e th e r b y
c o v a le n t b o n d
e x a m p le s : d ia m o n d , g r a p h it e , S iO 2
5.4 Phase
Diagram
Learning Outcomes :

At the end of this lesson students should be able to:

(a) Define phase .

(b) Sketch the phase diagram of H2O and CO2.

(c) Define triple point and critical point.

(d) Explain the anomalous behaviour of H2O.

(e) Describe the changes in phase with respect to

i. temperature (at constant pressure)

ii. pressure (at constant temperature).


Phase is a homogeneous part of a system
in contact with other parts of the
system but separated from them by a
well-defined boundary
Phase Diagram is a diagram that describes the
stable phases and phase changes of a
substance as a function of temperature and
pressure
used to predict the phase that exist under a
certain temperature and pressure
(i) Phase Diagram of H2O
B C

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Regions of the diagram

- The diagram has three main regions :


Solid, liquid and gas

- Each region corresponds to one phase of the substance.

- A particular phase is stable for any combination of pressure


and temperature.

- Any point along a line shows the pressure and temperature


at which the two phases exist in equilibrium.

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Important Points
1. Point T :
- Known as the triple point
- Triple point is the point at which the vapour, liquid and
solid states of a substance are in equilibrium.
- Triple point for water is 0.01C and 0.06 atm.

2. Point C :
- Known as the critical point
- Critical point is the point on a phase diagram at which
the vapour cannot be condensed to a liquid.
- The liquid gas line ends at the critical point.
- Above the critical point, the liquid cannot be
distinguished from its vapour form.

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(ii) Phase Diagram of CO2
B C

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TRIPLE POINT

At point T, the triple point; solid, liquid and


vapour are in equilibrium
CO2(s) CO2(l) CO2(g)

Triple point for CO2 is at 5.2 atm pressure and


temperature 57 OC.


for most compounds, the TB curve slant to
the right because solid is denser than liquid

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ANOMALOUS BEHAVIOR OF H2O

The phase diagram for water is not typical.


The melting temperature line , TB , slopes
slant to the left (negative slope)
i.e. the melting temperature decreases with
pressure.

This is because ice is less dense than water,


the solid occupies more space than the liquid.
An increase in pressure, favours the
formation of liquid H2O.( the phase that occupy
less space)
Thus, the higher the pressure, the lower the

temperature at which solid water melts.


Exercise:

a) Describe the phase change when carbon


dioxide undergoes isobaric heating at 5.2 atm
pressure
Exercises:
b) Describe the phase change when pressure is
applied to water isothermally at 0.01 C