Physical Chemistry
a review
Chemistry
• Deals with the study of the
structure of matter and changes it
undergoes.
• From French “alkemie”.
• From Arabic “al-kimia”, which
means “the art of transformation”.
Ani
2
5 Traditional Branches of Chemistry
Chemistry
Inorganic Organic Analytical Physical
Biochemistry
Chemistry Chemistry Chemistry Chemistry
Qualitative Quantitative
Analysis Analysis
Ani
deals with the study of physical properties and structure of matter
3
Some Notable Scientists
• Democritus
– first to conceive matter in the form of particles, which
he called atoms.
• Antoine Laurent Lavoisier
– regarded as the Father of Modern Chemistry
• Germain Hess
– Father of Thermochemistry
• George Davis
– Father of Chemical Engineering
• Arthur D. Little
– coined the term “unit operation”
E
4
States of Matter
Ani
5
States of Matter
Q
6
Problem from Reviewer
10. The simplest state of matter is
a. solid
b. liquid
c. gas
d. plasma
E
7
5th State of Matter
• Bose-Einstein Condensate (BEC)
– Named for the theorists Satyendra Nath
Bose and Albert Einstein who predicted its
existence
– It is an unusual state of matter that arises
because of quantum mechanical effects on a
collection of entities called bosons.
– Examples of materials containing Bose- Ani
Einstein condensates are superconductors E
and superfluids. 8
Ani
9
Properties of Matter
10
Changes in Matter
Q 11
Example Questions
1. The specific volume of a substance is the volume per gram of
b
substance. Specific volume is an example of
a. a chemical, extensive property c. a chemical, intensive property
b. a physical, intensive property d. a physical, extensive property
d 2. Which of the ff. is a chemical property of a slice of chocolate cake?
a. mass b. temperature c. volume d. dietary calories
d 3. Which of the following is a physical property?
a. corrosiveness b. explosiveness c. toxicity d. temperature
d 4. Which of the following is an extensive property of a bubble of air?
a. density b. temperature c. percent oxygen d. radius
Ani
b 5. Which of the following is an intensive property?
a. mass b. density c. volume d. number of atoms
Q 12
Example Question
Dalton viewed chemical change as:
a. creation and destruction of
atoms
b. a change of atoms from one type
into another
c. a rearrangement of atoms
Ani
d. a nuclear exchange
13
Gases
• Ideal gas
–High T, low P ( P < 1 atm)
–Does not exist
• Real gas
–Extremely high P
–Extremely low T
14
Kinetic Theory of Gases
• Gases are composed of molecules whose size is
negligible compared with the average distance
between them.
• The molecules of the gas are in rapid, random
motion, with uniform velocity.
• Collisions between gas molecules and the walls
of a container are perfectly elastic.
• There are no intermolecular attractive forces.
• The average kinetic energy of a molecule is
proportional to the absolute temperature. 15
Gas Laws
Ideal Gas Law:
16
Gases
• STP (Standard Temperature Pressure)
P = 1 atm; T = 0oC; Vm = 22.4 L/mol
• SATP (Standard Ambient Temperature Pressure)
P = 1 bar; T = 25oC
Q
17
Problem from Reviewer
1. Which of the following statement is CORRECT about
ideal gas?
a. The pressure of the gas is equal to the total kinetic
energy of the molecules in a unit volume of the gas
b. The product of pressure and volume of the gas is
always constant
c. The average kinetic energy of molecule of the gas is
proportional to its absolute temperature
d. The average kinetic energy of molecule of the gas is
proportional to the square root of its absolute
temperature
Q
18
Problem from Reviewer
6. Which of the following exists as gas at room
temperature?
a. Br2
b. Ga
c. I2
d. None of the these
Q
19
Problem from Reviewer
For numbers 2 and 3
A gas mixture has a density of 1.0628 g/L at 30oC and 740
torr.
2. What is the possible component of the mixture?
a. CO2 (44) – O2 (32)
b. Ne (20) – Ar (40)
c. He (4) – NH3 (17)
d. Ar (40) – Kr (84)
3. What is the fraction of the lighter gas in the mixture?
a. 0.18 b. 0.36 c. 0.64 d. 0.82
Q
20
Problem from Reviewer
4. For ideal gas possessing only translational
energy, the following relationships are valid
except
a. Cp = 2.5R
b. Cp = Cv – R
c. Cv = 1.5R
d. Cp/Cv = 1.67
Q
21
Problem from Reviewer
5. Calcium carbonate decomposes upon heating to
form CO2 gas according to the following reaction:
CaCO3 (s) → CaO (s) + CO2 (g)
What volume of CO2 gas collected over water at
25oC and 740 mm Hg is obtained from 2.875 grams
of CaCO3? Molar mass of CaCO3 = 100 g/mol and
vapor pressure of H2O at 25oC = 23.756 mm Hg.
a. 0.69 L b. 0.72 L c. 0.75 L d. 0.78 L
Q
22
Problem from Reviewer
9. Absolute zero maybe regarded
as that temperature at which
a. All gases become liquids
b. Molecular motion ceases
c. All substances are solids
d. Water freezes
23
Graham’s Law
Q
24
Problem from Reviewer
14. Nitrogen gas escapes through a pinhole in
68.4 seconds. Under the same conditions, a
gaseous compound with the empirical formula
CH2 escapes in 83.8 seconds. What is its
molecular formula?
a. C2H4
b. C3H6
c. C4H8
d. C5H10
Q
25
Problem from Reviewer
11. At what temperature will the velocity of CO2
molecules equal the velocity of oxygen
molecules at 0oC?
Distribution of Molecular Speeds
a. 102 C
o
b. 632oC
c. 132oC
d. 125oC
Ani
26
Molecular Weight Determination
• Method of Limiting Density
Q E
27
Problem from Reviewer
For numbers 12 and 13
The density of a saturated hydrocarbon containing 80% w/w
carbon was measured against pressure at 20oC according to the
following data:
ρ, g/L 0.298 0.692 1.188 1.784 2.491
P, atm 0.2 0.4 0.6 0.8 1.0
12. What is the exact molecular weight (g/mol) of the gaseous
hydrocarbon?
a. 29.675 b. 30.187 c. 30.891 d. 31.042
13. What is the molecular formula of the gas?
a. CH4 b. C2H6 c. C4H8 d. C5H10
28
Molecular Weight Determination
• Vapor Density Method
– Jean Baptiste André Dumas
29
Molecular Weight Determination
• Regnault Method
– Henri Victor Regnault
– Determines molecular weight of gases at
room temperature
– 300-500-mL dry gas bulb is evacuated and
weighed
– The bulb is filled with gas and weighed
– The bulb is then filled with a liquid of known
density and weighed Q
30
Problem from Reviewer
For numbers 7 and 8
The following data were obtained from the molecular
weight determination of a mixture of CO and CO2 using
Regnault’s Method at 25oC and 1 atm:
Weight of dry bulb = 37.2564 g
Weight of bulb + CO-CO2 mixture= 37.5265 g
Weight of bulb + H2O = 215.8819 g
7. What is the molecular weight (g/mol) of the mixture?
a. 31 b. 37 c. 43 d. 49
8. What is the mole percentage of CO2 in the mixture?
a. 0.22 b. 0.28 c. 0.44 d. 0.56
Q
31
Problem from Reviewer
15. If a given gas has a compressibility factor,
Z>1, this means that _________ exists between
the molecules of gases
a. attractive forces
b. repulsive forces
c. negligible forces of attraction
d. negligible repulsive forces
Q
32
Problem from Reviewer
16. The van der Waals constants a and b
for Ne gas are 0.02138 Pa∙m6∙mol-2 and
1.709x10-5 m3∙mol-1, respectively. What is
the critical temperature (K) of the gas?
a. 10 b. 25 c. 30 d. 45
33
Liquids
• From the kinetic theory viewpoint, a liquid
may be considered as a continuation of
the gas phase into a region of small
volumes and very high molecular
attractions
34
Liquid Viscosity
Q E
35
Problem from Reviewer
Q
36
Example Problem
The time efflux of water through an Ostwald
viscosimeter is 1.52 minutes. For the same
volume of an organic liquid of density 1.10
g/mL, the time is 2.25 minutes. Find its absolute
viscosity at 20oC. The absolute viscosity of water
at 20oC is 1 cP.
a. 1.63 cP b. 3.67 cP c. 5.89 cP d. 7.45 cP
Ani
Q
37
Problem from Reviewer
19. Fluids whose viscosity increases as
shear rate increases.
a. Dilatant
b. Pseudoplastic
c. Newtonian
d. Bingham plastic
Q
38
Problem from Reviewer
21. Fluids whose viscosity increases with time at
constant shear rate.
a. Inviscid
b. Rheopectic
c. Thixotropic
d. Pascalian
Q
39
Problem from Reviewer
23. What happens to the molecules in a liquid
when the liquid is heated and vapor starts to
form?
a. The intramolecular forces between liquid
molecules are disrupted
b. The intermolecular forces between liquid
molecules are disrupted
c. Kinetic energy is removed from the system
d. London forces become stronger
40
Liquid Viscosity
Q
41
Example Problems
1. A steel ball of density 7.90 g/mL and 4mm
diameter requires 55 sec to fall a distance of 1
meter through a liquid of density 1.10 g/mL.
Calculate the viscosity of the liquid in Pa·s .
a. 1.00 b. 3.26 c. 5.26 d. 7.89
2. Referring to the previous problem, what is the
viscosity in Pa·s of an unknown liquid with a mass
of 19.2 grams per 25 mL that required 23 seconds
to fall the same distance?
a. 4.31 b. 3.31 c. 2.43 d. 1.43
Q
42
Problem from Reviewer
17. Generally, viscosity of gases _______ as
temperature increases.
a. remains constant
b. increases
c. approaches unity
d. decreases
Ani
Q
43
Problem from Reviewer
44
45
46
Surface Tension
• Surface tension is a property of
the surface of a liquid that causes
it to behave as an elastic sheet.
• Each molecule is pulled equally in
all directions by neighboring liquid
molecules, resulting in a net force
of zero. E
47
Capillary Rise Method
• Capillary action is the spontaneous
rising of a liquid in a narrow tube.
Two difference forces are
responsible for this property:
– Cohesive forces – the intermolecular
forces among the molecules of the
liquid.
– Adhesive forces – the forces between
the liquid molecules and their
container.
Q E
48
Example Problem
Acetone with a density of 0.792 g/mL rises
to a height of 9.39 cm at 20oC in a capillary
tube, which has a radius of 0.065 mm.
Calculate the surface tension of acetone
from these data in dynes/cm
a. 10.32
b. 23.71
c. 43.56
d. 50.23
49
du Noüy Ring Method
• Tensiometer is the device used, which was developed in
Rockefeller Institute for Medical Research
proposed by Pierre Lecomte du Noüy
• Pierre Lecomte du Noüy
• The fundamental equation is
where: m = weights needed for the restoration of tensiometer’s
horizontal position
L = mean circumference of the ring
E
α = correction factor
50
Solids
• These have definite shape and volume
• These are rigid and exhibit certain
hardness
– Crystalline
• Arranged orderly
– Amorphous
• No definite form
51
The Six Crystal Systems
Q
52
Problem from Reviewer
22. Silver (107.87 g/mol) crystallizes with a face-
centered cubic unit cell. The radius of a silver
atom is 0.144 nm. Calculate the density of solid
silver.
a. 24.8 g/mL
b. 21.2 g/mL
c. 15.7 g/mL
d. 10.6 g/mL Ani
Q
53
Problem from Reviewer
24. Fe crystallizes in a body-centered cubic
lattice. The density of iron is 7.86 g/cm3.
Calculate the atomic radius of iron in
Angstrom.
a. 1.24 Å
b. 2.48 Å
c. 0.62 Å
Ani
d. 2.02 Å
54
Colligative Properties of Solutions
(Electrolyte Solutions)
Reverse Osmosis
Ani
Q
55
Problem from Reviewer
25. One colligative property of solutions is its
freezing point depression. Which observation
will show that the solute is an electrolyte
(ΔTf/m)?
a. is not a constant
b. is not Kf
c. is less than Kf
d. is greater than Kf
Q
56
Problem from Reviewer
26. A 0.2 m aqueous solution of KCl freezes
at -0.680oC. The osmotic pressure in atm at
0oC is
a. 9.8
b. 16.3
c. 8.2
d. 10.8
Q
57
Problem from Reviewer
27. Which of these 0.1 m solutions will give
the highest boiling point at 1 atm?
a. Table salt solution
b. Sugar solution
c. Barium chloride
d. Potassium chloride
Q
58
Problem from Reviewer
28. A solution of 0.72% w/w HCl freezes at
-0.706oC. Calculate the apparent molecular
weight (g/mol) of HCl.
a. 38.2
b. 37.8
c. 37.1
d. 36.5
Q
59
Problem from Reviewer
29. A 0.01 molal solution of K3Fe(CN)6
freezes at -0.062oC. What is its apparent
degree of dissociation?
a. 25.9%
b. 47.2%
c. 67.2%
d. 78%
Q
60
Problem from Reviewer
33. Which of the following statements about colligative
properties is TRUE?
a. Both vapor pressure and freezing point INCREASE
when a non-volatile solute is added to a solvent.
b. Both freezing point and boiling point INCREASE when
a non-volatile solute is added to a solvent.
c. Both vapor pressure and boiling point DECREASE
when a non-volatile solute is added to a solvent.
d. Colligative properties depend only upon the NUMBER
of solute particles in a solution and not upon their
identity.
61
Chemical Equilibrium
62
Use of the Equilibrium Constants
• Qualitatively interpreting the equilibrium
constant.
• Predicting the direction of reaction.
• Calculating equilibrium concentrations.
63
Chemical Equilibrium
Le Chatelier’s Principle (by Henry-Louis Le Chatelier) - when a
system in chemical equilibrium is disturbed by a change of
temperature, pressure, or a concentration, the system shifts in
equilibrium composition in a way that tends to counteract this change of
variable
N2 (g) + 3H2 ⇌ 2NH3 (g) +45kJ
1. Changing concentrations
dec concn of prod : favors forward rxn
inc concn of reac : favors forward rxn
2. Changing pressures/volumes
inc P dec V (favors lesser gas molecules)
dec P inc V (favors more gas molecules)
3. Changing temperatures
inc T favors endothermic
dec T favors exothermic Q 64
Problem from Reviewer
44. PCl5 (g) dissociates into PCl3 (g) and Cl2 (g)
when heated to 250oC and 1 atm. If the density
of the gas mixture at equilibrium is 4.4 g/L, the
fraction of PCl5 (g) dissociated is
a. 0.103
b. 0.328
c. 0.725
d. 0.209
Q
65
Problem from Reviewer
45. For the process C (s) + O2 (g) ⇌ CO2 (g),
it is found that ΔG at a given temperature
is -10 kcal/mol. Which statement is correct
at this temperature?
a. The system is in equilibrium
b. CO2 will be formed spontaneously
c. CO2 will decompose spontaneously
d. The process will proceed reversibly Q
66
Problem from Reviewer
46. At 300 K and 1 atm, CO2 is 40% dissociated
to CO and O2. Its percentage dissociation when
the pressure is increased to 2 atm is
a. 0.350
b. 0.335
c. 0.425
d. 0.375
Q
67
Problem from Reviewer
47. For a chemical reaction in a state of
equilibrium, a decrease in temperature will
a. Favor the reaction that is exothermic
b. Favor the reaction that is endothermic
c. Have no effect on the system
d. Increase the equilibrium constant of the
system
Q
68
Problem from Reviewer
49. In a chemical reaction, equilibrium has been
established when the _________.
a. opposing reaction ceases
b. concentrations are equal
c. reaction ceases to generate heat
d. net velocities of reactions is zero
Q
70
Phase Equilibria
• One Component Systems
–Clapeyron equation
–Clausius-Clapeyron equation
–Trouton’s Rule
Q
72
Example Problem
The densities of liquid and solid mercury are
13.7 and 14.19g/mL respectively at a
melting point of -38.87oC. The heat of fusion
of mercury is 566 cal/mol. Determine the
change in melting point per atmospheric
change (K/atm).
a. 0.0506 b. 0.506 c. 0.560 d. 0.00506
Use Clapeyron equation Ani
Q
73
Problem from Reviewer
40. The vapor pressure of solid CO2 is 76.7 mm
Hg at -103oC and its normal sublimation point is
-78.5oC. What is the heat of sublimation in
cal/mol of CO2?
a. 6061
b. 6160 Phase Equilibria
c. 6610 Clausius-Clapeyron equation
d. 6801 Ani
Q
74
Problem from Reviewer
48. The dissociation constant for liquid water into
hydrogen and oxygen gas at 1227oC is 1.90 x 10-11
and it is 3.90 x 10-19 at 727oC. The heat of reaction
of the following reaction is:
H2 (g) + ½ O2 (g) ⇌ H2O (l)
a. -442 kJ/mol
b. -221 kJ/mol
c. 221 kJ/mol
d. 442 kJ/mol
Q
69
Problem from Reviewer
50. For the reaction:
O2 (g) ⇌ 2O (g) ln Kp = -27.55 at 900 K
ΔH = 67850 + 1.85 T – 0.321 x 10-3 T2, cal/mol
Find the extent to which O2 (g) will be dissociated
into atoms at a temperature of 4000 K at 1 atm.
a. 60%
b. 70%
c. 80%
d. 90%
71
Example Problem
The normal boiling point of toluene is
110.62oC. Assuming that toluene obeys
Trouton’s rule, calculate its heat of
vaporization.
a. 6078 cal/mol
b. 7045 cal/mol
c. 8059 cal/mol
d. 9067 cal/mol
75
Phase Equilibria
• Ideal Solutions
– Solute-solute, solvent-solvent and solute-solvent
interactions are very similar
– Solute is nonvolatile
• Raoult’s law: Psolution = xsolvent Posolvent
• Modified form of Raoult’s law (liquid-liquid solutions,
both components volatile)
PT = PA + PB = xAPoA + xBPoB
Q
76
Problem from Reviewer
37. The vapor pressure of a liquid
a. Always increases with temperature
b. Always decreases with temperature
c. Is dependent of temperature
d. Increases only up to boiling point
Q
77
Problem from Reviewer
38. A solvent-water mixture is to be distilled at
95oC. The vapor pressure of the solvent at this
temperature is 130 mm Hg and that of water is 640
mm Hg. The solvent is immiscible in water and has a
molecular weight of 150 amu. The weight of the
solvent in kg that will be carried over in the
distillate with 200 kg of water is
a. 358.73
b. 423.57
c. 338.54
d. 524.63
78
Phase Equilibria
• Real solutions (nonideal solutions)
– Solvent has special affinity for solute
– Pobserved < P from Raoult’s law
The relationship between gas pressure and the
concentration of a dissolved gas in a solvent is given
by Henry’s law: S = kH P
Q
79
Problem from Reviewer
39. The law relating the solubility of
the gas to its pressure is called
a. Raoult’s law
b. Distribution law
c. Henry’s law
d. Arrhenius law
Q
80
Problem from Reviewer
41. Dry air is bubbled through 25.0 L of water at
a rate of 15 L (STP) per minute. The air leaving
the liquid is saturated with water at 25oC and
1.5 atm. How long will it take for all the water to
vaporize?
a. 32.9
b. 67.8
c. 79.1
d. 80.7
Q
81
Problem from Reviewer
42. Ethanol is to be used in an automobile
carburetor that is adjusted to give a 9:1 air-fuel
mass ratio. If the temperature in the manifold is
60oF and the pressure is atmospheric, what
percentage of the alcohol will be evaporated
assuming that equilibrium between vapor and
liquid is reached? Vapor pressure of ethanol at
60oF is 33.75 mm Hg.
a. 56% b. 76% c. 66% d. 90%
Q
82
Problem from Reviewer
43. When gaseous ammonia is dissolved in water, the
resulting solution does not obey Henry’s law. Which of the
following best explains why this solution does not obey
Henry’s law?
a. All of the NH3 that initially dissolves in the water rapidly
escapes from the solution because NH3 is a gas at room
temperature
b. NH3 reacts with the solvent to produce ammonium and
hydroxide ions
c. NH3 is not soluble in water because it is a non-polar
molecule
d. The hydrogen bonding between ammonia molecules is so
strong that NH3 cannot be dissolved in water
83
Electrochemistry
• Electrochemistry
– study of interrelationships between electricity
and chemical reactions
• Electrochemical cell
– generates voltage and current from chemical
reactions
– Galvanic cell and Electrolytic cell are the two
types
Q E
84
Problem from Reviewer
30. All the half-cell potential (Eo) use the
______ as the reference.
a. hydrogen electrode
b. oxygen half-cell
c. carbon half-cell
d. arbitrarily net zero point
Q
85
Problem from Reviewer
31. An electrochemical cell in which
chemical reaction is forced to occur by the
application of an outside source of energy
is
a. Galvanic
b. Electrolytic
c. Electrical
d. Chemical Q
86
Problem from Reviewer
32. The more negative the value of Eo, the
more likely the reaction is to proceed from
a. left to right
b. right to left
c. either way
d. can’t be determined
Q
87
Problem from Reviewer
34. Consider the following standard reduction
potentials:
Half reaction Eo, V
Fe3+ (aq) + e- ⇌ Fe2+ (aq) 0.77
H2O2 (aq) + 2e- ⇌ 2OH- (aq) 0.88
For a given voltaic cell, calculate the Fe2+ concentration
that would be needed to produce a cell potential equal
to 0.16 V at 25oC when [OH-] = 0.10 M, [Fe3+] = 0.50 M
and [H2O2] = 0.35 M.
a. 0.20 M b. 0.40 M c. 0.60 M d. 0.80 M Q
88
Example Question
Given the following reduction potentials
Zn2+ (aq) + 2e- ⇌ Zn (s) Eo = -0.76 V
Fe3+ (aq) + e- ⇌ Fe2+ (aq) Eo = 0.77 V
Determine whether the following cell
reaction is spontaneous or not.
Zn2+ (aq) + 2 Fe2+ (aq) Zn (s) + 2 Fe3+ (aq)
Q
89
Problem from Reviewer
35. A dilute acidic aqueous solution of Na2SO4 is
electrolyzed between platinum electrodes for 3.75
h with a current of 2.83 A. What volume of SO2 gas,
saturated with water vapor at 25oC and at a total
pressure of 742 mm Hg would be collected at the
anode?
a. 1.281 L
b. 2.562 L
c. 5.124 L
d. 10.248 L
Q
90
Problem from Reviewer
36. An aqueous solution of gold nitrate is
electrolyzed with a current of 0.555 A until 1.32
g of gold has been deposited on the cathode. If
the atomic weight of Au is 197 amu, determine
the duration of the electrolysis.
a. 65.43 min
b. 23.67 min
c. 58.28 min
d. 60.00 min
91
Thank You for
Listening