Lecture 06

Contents 1. Vapor pressure and changes of state 2. Vapor pressure of solid and liquid water 3. Phase Diagrams 4. Types of solids 5. Crystal Structures

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Evaporation and Vapor Pressure Evaporation Evaporation process is a surface phenomenon. Some molecules have enough kinetic energy to escape.

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Evaporation and Vapor Pressure Evaporation If the container is closed, an equilibrium is reached where an equal number of molecules return to the surface. The pressure of this equilibrium is called the vapor pressure.

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Evaporation and Vapor Pressure

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Vapor pressure and changes of state Vapor Pressure

Rate of evaporation equals the rate of condensation

Rate of evaporation

Rate

Rate of condensation

Time
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Vapor pressure and changes of state

Liquid ethanol Equilibrium vapor pressure

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Vapor pressure
Liquids with high vapor pressure are said to be volatile.

The vapor pressure is determined by the size of the intermolecular forces in the liquid. High intermolecular Low vapor forces pressure The vapor pressure increases with temperature. Substances with larger molar masses have relatively low vapor pressure. HOH CH3 O CH3 18
Prof. Dr. Mamdouh A. Abdel Rahim

46
Lecture 6

Vapor pressure
Vapor Pressure (atm)
Diethyl ether
34.6

1.00 0.75 0.50 0.25 0 0

Ethyl alcohol
78.4

water
100

C2H5 - O - C2H5 C2H5 - O - H H - O - H

20

40

Temperature

60

80

100
Lecture 6

Prof. Dr. Mamdouh A. Abdel Rahim

Vapor pressure Relation between v.p. and temperature Clausius-Clapeyron Equation

ln (P) = Hvap R T C

Hvap R

1 + C T

is the heat of vaporization is the universal gas constant is the absolute temperature is a constant characteristic of a given gas
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Vapor pressure Example: The vapor pressure of water at 25C is 23.8 torr, and the heat of vaporization is 43.9 kJ/mol. Calculate the vapor pressure of water at 50C. Solution:

Hvap + C ln (PT ) = 1 RT1 Hvap + C ln (PT ) = 2 R T2

Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Vapor pressure

C = ln (PT1 ) + C = ln (PT ) + 2 ln (PT1 ) +

Hvap
R T1 Hvap R T2

Hvap
R T1

= ln (PT2 ) +

Hvap

ln (PT ) - ln (PT ) = 1 2

Hvap
R T2

R T2 Hvap R T1
Lecture 6

Prof. Dr. Mamdouh A. Abdel Rahim

Vapor pressure

(PT1 ) Hvap ln = (PT2 ) R

1 T2

1 T1

43.9 kJ/mol 23.8 torr 1 1 ) ( ln = 323 K 298 K (PT ) 8.314 J/K mol 2 43900 J/mol 23.8 torr 1 1 ) ( ln = 323 K 298 K (PT ) 8.314 J/K mol 2

PT2 = 93.7 torr

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Change of state A substance is melting while it changes from a solid to a liquid. is freezing while it changes from a liquid to a solid. such as water has a freezing (melting) point of 0C. and has a boiling (condensation) point of 100C.
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Change of state
50 g H2O(l) 100C 50 g H2O(l) 25C 50 g H2O(s) 0 C

Cooling

Heating

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

140 120

Temperature (C )

100 80 60 40 20 0 -20 Ice and water Ice

Boiling point

Water and steam

Steam

Water Heat of fusion Melting point

Heat added
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Vapor pressure of solid and liquid water

10

Pvap (torr)

Melting Vapor pressure point of liquid Vapor pressure of solid

-5

0 Temperature (C )
Prof. Dr. Mamdouh A. Abdel Rahim

+5
Lecture 6

Vapor pressure of solid and liquid water 10 10 Case 1: A temperature at which the 5 5 vapor pressure of the solid is greater than that of the liquid 0 0 0 -5 5 0
Pvap (torr) P vap (torr)

Temperature Temperature ( ( C C) )

+ +5 5

water vapor

Solid water

Liquid water
Prof. Dr. Mamdouh A. Abdel Rahim

Liquid water
Lecture 6

Vapor pressure of solid and liquid water 10 10 Case 2: A temperature at which the 5 5 vapor pressure of the solid is less than that of the liquid 0 0 0 -5 5 0
Pvap (torr) P vap (torr)

Temperature Temperature ( ( C C) )

+ +5 5

Solid water

Liquid water

Solid water
Lecture 6

Prof. Dr. Mamdouh A. Abdel Rahim

Vapor pressure of solid and liquid water 10 10 Case 3: A temperature at which the 5 5 vapor pressure of the solid is equal to that of the liquid
Pvap (torr) P vap (torr) 0 0 -5 5 + 0 +5 5 0 Temperature Temperature ( ( C C) )

Solid water

Liquid water

Solid water

Liquid water
Lecture 6

Prof. Dr. Mamdouh A. Abdel Rahim

Vapor pressure of solid and liquid water The normal melting point It is the temperature at which the solid and the liquid states have the same vapor pressure under conditions where the total pressure is 1 atm. The normal boiling point It is the temperature at which the vapor pressure of the liquid is exactly 1 atm.

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Phase Diagrams A phase diagram is describing the sate of equilibrium between the state of matter at different pressure and temperature. A phase diagram is a graphical way to predict the effects of pressure and temperature on the phase of a substance . Every substance has its own phase diagram.

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Phase Diagram of water

218

Pressure (atm)

Critical point melting freezing

Liquid
vaporization condensation

Solid
1 Triple point

0.006 sublimation deposition 00

Vapor
374
Lecture 6

0.0025

Prof. Dr. Mamdouh A. Abdel Rahim

0.01 100 Temperature

Phase Diagram of water

Pressure (atm)

Liquid Solid
1 Expt 3 Expt 2

Expt 4

Expt 1

Vapor Temperature
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Phase Diagrams

The Critical Point

- The critical temperature, Tc: is the temperature above which the vapor can not be liquefied by any pressure. - The critical pressure, Pc: is the pressure required to cause liquefaction at the critical temperature.

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

The solid state

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

The solid state Types of solids Four types of solids could exist

Ionic Solids NaCl MgO CaCO3

Molecular Solids I2 H2O

Macromolecular Solids C SiO2

Metallic Solids Na Mg Fe
Lecture 6

Prof. Dr. Mamdouh A. Abdel Rahim

Ionic solids

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Ionic solids NaCl and MgO melt without any change in chemical composition. Solids with polyatomic ions decompose rather than melt. Hydroxides Metal oxide H2O gas Carbonates Hydrated Salts

Metal oxide

CO2 gas

Loss some water of crystallization

Lecture 6

Prof. Dr. Mamdouh A. Abdel Rahim

Molecular solids They are solids at room temperature. Have strong intermolecular forces. They include non-polar substances include high molecular mass as: I2 naphthalene Ice

M.wt. = 254 M.wt. = 128 Urea

Lecture 6

Others contain hydrogen bonds as:

Prof. Dr. Mamdouh A. Abdel Rahim

Macromolecular solids Atoms are held together by a two dimensional network of electron-pair bonds, such as: X X X X X X X X X X X X X Y X Y X Y X Y X Y X Y

Element
Prof. Dr. Mamdouh A. Abdel Rahim

Compound
Lecture 6

Macromolecular solids

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Metallic solids They are good conductors of heat, ductile and malleable. Their surfaces are good reflectors of light. They are good conductors of electricity due to the moving free see of electrons.
ee-

+ +
ee-

+
e+

eee-

+ e+

e- 2+ e- 2+ e 2+ eeee e e- 2+ - 2+ e 2+ e e- 2+ e 2+ 2+ eee-

e-

Na metal
Prof. Dr. Mamdouh A. Abdel Rahim

Mg metal
Lecture 6

The lattice energy of Mg is greater than that of Na.

Crystal Structure A metallic crystal is pictured as containing spherical atoms packed together. The spheres are packed using the available space, this arrangement is called closest packing

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Crystal Structure The spheres are packed 6 1 in layers in which each 5 2 sphere is surrounded by 4 3 six other spheres. A sphere in the first layer touches three spheres in the layer above it, and similarly it touches three spheres in the layer below it, plus six spheres in its own layer, making a total of twelve.
Prof. Dr. Mamdouh A. Abdel Rahim

8 9 7 5 6 4 1 3 2 11 12 10
Lecture 6

Crystal Structure The various arrangements:

3rd layer 2nd layer 1st layer

A B A

3rd layer 2nd layer 1st layer

C B A

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Crystal Structure The a b a arrangements: a b a hexagonal closest packed (hcp) structure

Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Crystal Structure The a b c arrangements: a b c a

face-centered cubic unit cell cubic closest packed (ccp) structure

Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

The net number of spheres in a unit cell Not shared

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

The net number of spheres in a unit cell Shared by two cells

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

The net number of spheres in a unit cell Shared by eight cells

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Simple Cubic

Number of spheres = 1 = 1 8 8
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Body-Centered Cubic Unit Cell

1/8 atoms at 8 corners

Number of spheres = 1 = 1+ 1= 2 1+ 8 8
Prof. Dr. Mamdouh A. Abdel Rahim

1 atom at center

Lecture 6

Face-Centered Cubic Unit Cell

Number of spheres = 1 1 + 8 = 6 2 8 3+ 1 = 4
Prof. Dr. Mamdouh A. Abdel Rahim

1/8 atoms at 8 corners 1/2 atom at 6 faces

Lecture 6

Unit Cells

Simple Cubic

Body-Center Cubic

Face-Center Cubic

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6

Crystal Structure Example: Silver crystallizes in a cubic closest packed structure. The radius of a silver atom is 1.44 (1 = 10-8 cm). Calculate the density of solid silver. Solution: The density is the mass per unit volume. We must find the volume of the unit cell and the net number of atoms it contains.
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

Crystal Structure r 2r r d d d d 4r d

(4r)2 = d2 + d2 = 2d2 d2 = 8 r2
Prof. Dr. Mamdouh A. Abdel Rahim

2d2 = 16 r2 d = r 8
Lecture 6

Crystal Structure Since the radius of a silver atom is 1.44 .

d = r 8 = 1.44 8 = 4.07
The volume of the unit cell = d 3
3 -23 cm3 67.4 6.74 10 = =

4 atoms of Ag occupy

6.74 10-23 cm3

Lecture 6

Prof. Dr. Mamdouh A. Abdel Rahim

Crystal Structure Atomic wt of Ag (107.9) is the mass of 1 mole 1 mole of Ag contains 6.022 1023 atoms 107.9 g is the mass of 6.022 1023 atoms 4 atoms mass of 4 atoms = 4 atoms 23107.9 g 6.022 10 atoms density = mass volume 4 atoms 107.9 g = 6.022 1023 atoms 6.74 10-23 cm3 = 10.6 g/cm3
Prof. Dr. Mamdouh A. Abdel Rahim Lecture 6

?g

the mass of

Thank you

Prof. Dr. Mamdouh A. Abdel Rahim

Lecture 6