In Class Review Feb - 9 Lecture - 10

Chapter 13
Physical Properties of Solutions
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
13.1 Types of Solutions
A solution is a homogeneous mixture of two or more substances.
A solution consists of a solvent and one or more solutes.
Solute: the component that is dissolved in solvent
-usually in smaller amount
Solvent: medium into which solutes are mixed
-usually in greater amount (usually liquid)
Types of Solutions
Solutions can be classified by the amount of solute dissolved.
An unsaturated solution can dissolve more solute at a specific

temperature.
Types of Solutions
A saturated solution contains as much solute as can be dissolved at
specific temperature
Solubility: amount (mass) of solute that forms saturated solution

with given mass/volume of solvent at specific temp
Types of Solutions
Supersaturated solutions contain more dissolved solute than is
present in a saturated solution and are generally unstable.
-formed by cooling saturated solution from a higher temperature
Saturated
Heat
Cools down
Supersaturated
https://www.youtube.com/watch?v=DVIkxKGR8wU
13.2 A Molecular View of the Solution Process: The
Importance of Intermolecular Forces
How is a solution formed?

-intermolecular forces are important in formation of a solution
Solid solute Liquid solvent Liquid solution
1) disruption of solute-solute interactions (like breaking a bond)

2) disruption of solvent-solvent interactions (like breaking a bond)
3) formation of solute-solvent interactions (like forming a bond)
The Importance of Intermolecular Forces
ΔH1 = disruption of solute-solute
ΔH2 = disruption of solvent-solvent
ΔH3 = formation of solute-solvent
ΔHsoln = enthalpy of solution = heat of solution
= ΔH1 + ΔH2 + ΔH3
exothermic
endothermic
endothermic
ΔHsoln > 0 (endothermic) if ΔH3 < ΔH1 + ΔH2

ΔHsoln < 0 (exothermic) if ΔH3 > ΔH1 + ΔH2
ΔHsoln < 0
Solutions of gases in liquids:
-ΔHsoln usually < 0 (exothermic)
=don’t need to break solute-solute interactions, so ΔH1 ~ 0
• Solubility of solute in a solvent can be predicted:

“like dissolves like” (in terms of IM forces)
-The more similar the IM forces (solvent vs solute), the more likely the solute
will dissolve
Ionic bond > hydrogen-bond > dipole-dipole > dispersion force
Ionic F-H F-H Polar Non-polar

compounds O-H O-H molecules molecules
N-H N-H
Some examples
=CCl4 dissolves in benzene (C6H6) (both nonpolar)
=H2O and methanol (CH3OH) are both polar and dissolve in
each other
• Two liquids that are soluble in each other in all proportions

=miscible (opposite is immiscible)
• Ions readily dissolve in polar solvent due to solvation by the

solvent molecules (and ionic compounds not very soluble in
nonpolar solvents)
• https://www.youtube.com/watch?v=PVL24HAesnc
• 6:38
Favorite Exam Question
Which of the following dissolves best in water?
a) Carbon dioxide
b) Sodium chloride
c) Methanol (CH3OH)
d) Benzene (C6H6)
All hydrocarbons are non-polar
e) Dimethyl ether (CH3OCH3)
Practice Example
Predict whether Vitamin B6 is water soluble or fat soluble:

13.3 Concentration Units
The amount(moles/grams) of solute relative to the amount

(moles/mass/volume) of solvent/solution is called concentration.
moles of solute
Molarity: molarity = M =
liters of solution
-unit mol/L
-varies with temperature
Mole fraction: the ratio of the number of moles of one component

to the total number of moles in a mixture
moles of A
mole fraction of component A =  A =
sum of moles of all components
mole percent = (mole fraction) x 100

-independent of temperature
Molality and Percent by Mass
Molality (m) is the number of moles of solute dissolved in 1 kg (1000

g) solvent:
moles of solute
molality = m =
mass of solvent (in kg)
Percent by Mass: ratio of mass of solute to the mass of the solution
times 100 (parts per hundred)
mass of solute
percent by mass =  100 %
mass of solute + mass of solvent
parts per thousand and the multiplier is 1000 (103)
ppm is parts per million and the multiplier is 1,000,000 (106)
others follow with a change in the multiplier only (ppt, ppb)
Conversions between concentration units
moles of solute
molarity = M =
liters of solution
moles of solute
molality = m =
mass of solvent (in kg)
moles of A
mass of solute
Practice Example
Determine the (a) molality, (b) percent by mass and (c) the ppm
concentrations of a solution prepared by dissolving 15.56 g of
glucose (C6H12O6; MW = 180.2 g mol–1) in 255 g of water.
𝑚𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑒 15.56 𝑔÷180.2 𝑔/𝑚𝑜𝑙

Molality = = = 0.339 𝑚
𝑘𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 0.255 𝑘𝑔
𝑔 𝑠𝑜𝑙𝑢𝑡𝑒 15.56 𝑔
% by mass = × 100 = × 100% = 5.75 %
𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 255 𝑔+15.56 𝑔
ppm = × 106 = × 106 = 5.75 × 104 ppm
ppb = × 109 = × 109 = 5.75 × 107 ppb
Conversions between concentration units
Strategy for solving these kind of problems:

1. write down what you’re starting with as a fraction
2. write down what your target is as a fraction
3. convert numerator to numerator, denominator to denominator
NOTES:
-use molar mass to convert between mass and mole
-use density to convert between mass and volume
-mass of solvent + mass of solute = mass of solution
-pay attention to the denominator which could refer to
solvent/solution and volume/mass/mole.
Practice Example mass of solute
Calculate the molality of a 10.0% aqueous NaCl solution:
Numerator
Denominator Mass of solution Mass of solute Mass of solvent
𝑚𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑒 0.171 𝑚𝑜𝑙 𝑁𝑎𝐶𝑙

Molality = = = 1.90 𝑚
𝑘𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 0.0900 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟
If molality of NaCl is 1.90 m, can you determine % for NaCl

in solution? Try it at home!
Practice Example mass of solute
Calculate the molarity of a 36.0% HCl solution
(MWHCl = 36.46 g mol–1; density of solution = 1.19 g mL–1):
36.0 𝑔 𝐻𝐶𝑙 𝑚𝑜𝑙𝑠 𝑜𝑓 𝐻𝐶𝑙
36.0 % = to
100 𝑔 𝐻𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐿𝑖𝑡𝑒𝑟𝑠 𝑜𝑓 𝐻𝐶𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑔
Numerator: 36.0 𝑔 𝑜𝑓 𝐻𝐶𝑙 ÷
? 36.46 𝑚𝑜𝑙 = 0.987 𝑚𝑜𝑙 𝐻𝐶𝑙
𝑔
Denominator: 100 𝑔 𝐻𝐶𝑙 soln ÷
? 1.19 𝑚𝐿 = 84.0 𝑚𝐿 = 0.0840 𝐿
𝑚𝑜𝑙
Molarity of HCl soln: 0.987 𝑚𝑜𝑙𝑠 𝐻𝐶𝑙 ÷ 0.0840 𝐿 = 11.8 𝑜𝑟 𝑀
𝐿
If molarity of a HCl solution is 11.8 M, can you determine %

for HCl in solution? (MWHCl = 36.46 g mol–1; density of solution
= 1.19 g mL–1) Try it at home!
A solution containing substance A (molar mass = 62 g mol–1) and B (molar mass = 48 g
mol–1) has a density of 1.12 g mL–1. The mole fraction of A in this solution is 0.26.
Find the molarity of A in the solution.
𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑚𝑜𝑙 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑚𝑜𝑙 𝑜𝑓 𝐴
= 0.26
𝑚𝑜𝑙 𝑜𝑓 𝐴 + 𝑚𝑜𝑙 𝑜𝑓 𝐵 𝑙𝑖𝑡𝑒𝑟𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑙𝑖𝑡𝑒𝑟𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Assume there is a total of 100 mols of the substance

𝑚𝑜𝑙 𝑜𝑓 𝐴 26 𝑚𝑜𝑙 𝑜𝑓 𝐴
= 0.26 𝑔 𝑔
100 𝑚𝑜𝑙𝑠 𝑜𝑓 (𝐴 + 𝐵) 26 𝑚𝑜𝑙 × 62 + 74 𝑚𝑜𝑙 × 48
𝑚𝑜𝑙 𝑚𝑜𝑙
26 𝑚𝑜𝑙 𝑜𝑓 𝐴
= 0.26 26 𝑚𝑜𝑙 𝑜𝑓 𝐴
100 𝑚𝑜𝑙𝑠 𝑜𝑓 (𝐴 + 𝐵)
5164 𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Answer: 5.64 M
= 0.26 26 𝑚𝑜𝑙 𝑜𝑓 𝐴
26 𝑚𝑜𝑙 𝑜𝑓 𝐴 + 74 𝑚𝑜𝑙 𝑜𝑓 𝐵 𝑔
5164 𝑔 ÷ 1.12
𝑚𝑙
26 𝑚𝑜𝑙 𝑜𝑓 𝐴 26 𝑚𝑜𝑙 𝑜𝑓 𝐴
20
4.6107 𝑙𝑖𝑡𝑡𝑒𝑟𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 4610.7 𝑚𝑙 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
A solution containing substance A (molar mass = 62 g mol–1) and B (molar mass = 48 g
mol–1) has a density of 1.12 g mL–1. The mole fraction of A in this solution is 0.26.
Find the molality of A in the solution.
𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑚𝑜𝑙 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑚𝑜𝑙 𝑜𝑓 𝐴
= 0.26
𝑚𝑜𝑙 𝑜𝑓 𝐴 + 𝑚𝑜𝑙 𝑜𝑓 𝐵 𝑘𝑔 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑘𝑔 𝑜𝑓 𝐵
Assume there is a total of 100 mols of the substance

𝑚𝑜𝑙 𝑜𝑓 𝐴 26 𝑚𝑜𝑙 𝑜𝑓 𝐴
= 0.26 𝑔 𝑔
100 𝑚𝑜𝑙𝑠 𝑜𝑓 (𝐴 + 𝐵) 26 𝑚𝑜𝑙 × 62 + 74 𝑚𝑜𝑙 × 48
𝑚𝑜𝑙 𝑚𝑜𝑙
= 0.26 26 𝑚𝑜𝑙 𝑜𝑓 𝐴
100 𝑚𝑜𝑙𝑠 𝑜𝑓 (𝐴 + 𝐵)
3552 𝑔 𝑜𝑓 𝐵
= 0.26 26 𝑚𝑜𝑙 𝑜𝑓 𝐴
26 𝑚𝑜𝑙 𝑜𝑓 𝐴 + 74 𝑚𝑜𝑙 𝑜𝑓 𝐵
1 𝑘𝑔
3552 𝑔 ÷
1000 𝑔
Answer: 7.32 m 21
13.4 Factors That Affect Solubility: Temperature
• Solubility of solids may increase, decrease or remain relatively

constant with increasing temperature
• Solubility of gases decreases with increasing temperature
WHY???
Temperature effect on solubility
Temperature effect due to heat of solution (and other factors):

-endothermic (ΔHsoln > 0)
Heat + (solute)undissolved ⇄ (solute)dissolved
= increase temperature, shift equilibrium to the right
• Le Chatelier’s Principle
= shift to the right ➔ more solute dissolves
• this is what we usually observe!
-exothermic (Δ Hsoln < 0)
(solute)undissolved ⇄ (solute)dissolved + heat
= increase temperature, shift equilibrium to the left
= shift to the left ➔ less solute dissolves
(precipitation!)
OTHER FACTORS often lead to unpredictable results
Pressure effect on solubility
Pressure greatly influences the solubility of a gas.
-doesn’t significantly affect solubility of a solid
-CO2 in a soda
gas + solvent ⇄ solution

-increase in pressure
-reaction moves to right
Pressure effect on solubility
Henry’s law states that the solubility of a gas (c) in a liquid is directly
proportional to the partial pressure (P) of the gas over the solution.
c = kP
c molar concentration of the gas solute in the solution (mol/L)

P pressure of gas over the solution(atm)
k proportionality constant called Henry’s law constant
k = c / P → c1 / P1 = c2 / P2 = k (constant temperature)
1 M / 2 atm = c2 / 4 atm
c2 = 2 M
13.5 Colligative Properties
Colligative properties are properties that depend on the number of

solute particles in solution, NOT depend on the nature of the solute
particles.
Colligative properties we focus are:

➢ vapor pressure lowering
➢ boiling point elevation
➢ freezing point depression
➢ osmotic pressure
Vapor Pressure Lowering
Solution containing volatile solvent (e.g. H2O) and nonvolatile solute (e.g. sugar)
-solvent is volatile and thus, has vapor pressure (VP)
-solute is nonvolatile and thus, has NO appreciable VP
-solute blocks surface sites

=fewer sites for qualified solvent particles to escape to vapor phase
(qualified solvent particles = particles at surface and has enough energy)
=fewer solvent particles enter vapor phase
=lower vapor pressure
-Solution vapor pressure is proportional to mole fraction of solvent (𝜒solvent)
Raoult’s law states that the partial pressure of a solvent over a
solution is given by the vapor pressure of the pure solvent times the
mole fraction of the solvent in the solution.
P1 = χ1P1°
P1 partial pressure of solvent from solution (vapor pressure of
solution)
P1° vapor pressure of pure solvent
χ1 mole fraction of solvent
Mole fraction: the ratio of the number of moles of one component

to the total number of moles in a mixture
moles of A
VP of pure solvent
No solvent Pure solvent
P1 = χ1P1°
Practice Example
CCl4 has VP = 100.0 torr (23 ℃) (MW = 154 g mol–1). It can dissolve
wax (C22H46; MW = 311 g mol–1). What is the VP at 23 ℃ of a
solution of 10.0 g wax dissolved in 40.0 g CCl4?
𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝜒solvent × 𝑃°𝑠𝑜𝑙𝑣𝑒𝑛𝑡
If both solute and solvent of a

solution are volatile, the vapor VP of pure benzene
pressure of the solution is the sum
of the individual partial pressures.
PA = χAPA° PB = χBPB°
Psolution = PA + PB
= χAPA° + χBPB°
χA+ χB = 1
VP of pure toluene
Benzene Toluene
Benzene Toluene
If χA = χB = 0.5, is PA = PB?
PA
PV=nRT PB
Which liquid is more volatile?

The more volatile, the weaker the IMFs
If A is more volatile than B, then 𝜒𝐴 in the vapor phase will be larger than 𝜒𝐴 in the
liquid phase (for every mixture of A and B)
-this is the basis for fractional distillation
The vapor pressure of acetonitrile, CH3CN, is 81.0 torr while that of acetone,
C3H6O, is 184.5 torr. What is the vapor pressure of a solution which contains 0.440
moles of acetonitrile and 0.560 moles of acetone (assume the mixture behaves as
an ideal solution)?
Psolution = χAPA° + χBPB°
𝟎.𝟒𝟒𝟎 𝟎.𝟓𝟔𝟎
Psolution = × 𝟖𝟏 + × 𝟏𝟖𝟒. 𝟓
𝟎.𝟒𝟒𝟎+𝟎.𝟓𝟔𝟎 𝟎.𝟒𝟒𝟎+𝟎.𝟓𝟔𝟎
Psolution = 𝟎. 𝟒𝟒 × 𝟖𝟏 + (𝟏 − 𝟎. 𝟒𝟒) × 𝟏𝟖𝟒. 𝟓
Ans: 139 torr

Boiling Point Elevation/Freezing Point Depression
Recall: BP = temperature where the vapor pressure (VP) of a
substance equals to the atmospheric pressure
AND: VP of solution is lower than VP of pure solvent
SO: a solution requires more energy (higher temp) than a pure solvent
to evaporate solvent to reach to atmospheric pressure
THUS: the BP of the solution will be GREATER than the BP of the
pure solvent
For freezing of a solution: solute inhibits formation of solid solvent
lattice, so must have lower temp to get that lattice to form
Solution
Pure H2O BP > 100 °C
BP 100 °C
FP 0 °C
-freezing point is lowered (freezing curve shifts to left) FP < 0 °C
-boiling point is elevated (vaporization curve shifts right)
-area occupied by liquid phase is increased
-liquid is stable over larger set of P/T conditions
Can calculate change in FP (ΔTf) or BP (ΔTb):

-change directly proportional to the molality concentration
∆Tf = Kfm ∆Tb = Kbm
∆Tf = Tf° – Tf ∆Tb = Tb – Tb°
ΔTf freezing point depression ΔTb boiling point elevation
Tf FP of solution Tb BP of solution
Tf° FP of pure solvent Tb° BP of pure solvent
Kf freezing point depression Kb boiling point elevation
constant (°C/m) constant (°C/m)
m molality of solute m molality of solute
NOTE: Kf and m are positive numbers, which means ΔTf or ΔTb

should be positive numbers(HIGH TEMP MINUS LOW TEMP)
Kf and Kb values will be provided in exams

Worked Example
Ethylene glycol [CH2(OH)CH2(OH)] is a common automobile antifreeze. It is
water soluble and fairly nonvolatile. Calculate (a) the freezing point and (b) the
boiling point of a solution containing 685 g of ethylene glycol in 2075 g of water.
Strategy Convert grams of ethylene glycol to moles, and divide by the mass of
water in kilograms to get molal concentration. Use molal concentrations and ΔTb
= Kbm and ΔTf = Kfm, respectively. The molar mass of ethylene glycol (C2H6O2)
is 62.07 g/mol. Kf and Kb for water are 1.86°C/m and 0.52°C/m, respectively.
Solution
(685 g C2H6O2)/(62.07 g/mol) = 11.04 mol C2H6O2
(11.04 mol C2H6O2)/(2.075 kg water) = 5.32 m C2H6O2
∆Tf = Tf° – Tf (a) ΔTf = Kfm = (1.86°C/m)(5.32 m) = 9.89°C
Tf = Tf° – ∆Tf The freezing point of the solution is (0 – 9.89)°C = – 9.89°C
∆Tb = Tb – Tb° (b) ΔTb = Kbm = (0.52°C/m)(5.32 m) = 2.8°C

∆Tb + Tb° = Tb The boiling point of the solution is (100.0 + 2.8)°C = 102.8°C
Worked Example 13.8
Quinine was the first drug widely used to treat malaria, and it remains the
treatment of choice for severe cases. A solution prepared by dissolving 10.0 g of
quinine in 50.0 mL of ethanol has a freezing point 1.55°C below that of pure
ethanol. Determine the molar mass of quinine. (The density of ethanol is 0.789
g/mL.) Assume that quinine is a nonelectrolyte.
Strategy Use ΔTf = Kfm to determine the molal concentration of the solution.
Use the density of ethanol to determine the mass of the solvent. The molal
concentration of quinine multiplied by the mass of ethanol (in kg) gives moles of
quinine. The mass of quinine (in grams) divided by moles of quinine gives the
molar mass. Kf for ethanol is 1.99°C/m.
Solution mass of ethanol = 50.0 mL × 0.789 g/mL = 39.5 g or 3.95×10−2

kg
Solving ΔTf = Kfm for molal concentration
m = ΔTf/Kf = (1.55C)/(1.99C/m) = 0.779 m

Worked Example 13.8 (2)
Solution The solution is 0.779 m in quinine (i.e., 0.779 mol of quinine/kg
ethanol solvent.)
[(0.779 mol quinine)/(kg ethanol)](3.95×10-2 kg ethanol) = 0.0308 mol quinine
molar mass of quinine = (10.0 g quinine)/(0.0308 mol quinine) = 325 g/mol
Think About It Check the result using the molecular formula of quinine:
C20H24N2O2 (324.4 g/mol). Multistep problems such as this one require careful
tracking of units at each step.
Osmotic Pressure
Osmosis is the selective passage of solvent

molecules through a semipermeable membrane
Osmotic Pressure
-start with solvent on left, solution on right

-as time goes by, solvent moves thru membrane
from left to right (higher concentration of solvent
on left, so moves to right to try to reach point
where both sides have similar concentrations)
Osmotic Pressure (2)
Osmotic pressure (π) of a solution is the pressure required to stop

osmosis
-directly proportional to molar concentration, M
π = MRT
π Osmotic pressure (atm)
M molarity (mol/L)
R gas constant (0.08206 L∙atm/mol∙K)
T absolute temperature (Kelvins)
K = °C + 273.15
Two solutions with same concentration have same
osmotic pressure = isotonic to each other
Worked Example 13.9
A solution is prepared by dissolving 50.0 g of hemoglobin (Hb) in enough water to
make 1.00 L of solution. The osmotic pressure of the solution is measured and found
to be 14.3 mmHg at 25°C. Calculate the molar mass of hemoglobin. (Assume that
there is no change in volume when the hemoglobin is added to water.)
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 50.0 g Hb
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
Look for this
1. Use π = MRT to calculate the molarity of the solution.

2. The solution volume is 1 L, can determine the number of moles of Hb
3. Things to be aware of: R = 0.08206 L∙atm/K∙mol, convert mmHg to atm
using 760 mmHg = 1 atm. Temperature in Kelvin
Solution
π = 14.3 mmHg/(760 mmHg/atm) = 1.88×10−2 atm
Rearranging π = MRT to solve for molarity we get,
M = π/RT = (1.88×10−2 atm)/(0.08206 L∙atm/K∙mol)(298.15 K) = 7.69×10−4

M
Thus, the solution contains 7.69×10−4 moles of hemoglobin (1 L solution).
molar mass of hemoglobin = (50.0 g)/(7.69×10−4 mol) = 6.50×104 g/mol
Think About It Biological molecules can have very high molar masses.
Electrolyte Solutions
FP or BP of solution depends on number of particles in solution
-nonelectrolyte: 1 mol glucose→ 1 mol in solution
-strong electrolyte: 1 mol NaCl→ 2 mol in solution
(AB) (1 mol Na+ and 1 mol Cl-)
-weak electrolyte: 1 mol HF → betw. 1 and 2 mol
(AB) in solution (partial dissociation)
Solution Ions Theoretical FP Actual FP

1.00 m NaCl Na+ (aq), = 0 ℃ – ΔTf –3.37 ℃
Cl– (aq) = 0 ℃ – (2.00 m)(1.86)
= –3.72 ℃
1.00 m (NH4)2SO4 2 NH4+ (aq), = 0 ℃ – ΔTf –3.6 ℃
SO42– (aq) = 0 ℃ – (3.00 m)(1.86)
= –5.58 ℃
Theoretical FP usually slightly lower than actual. Why?
Theoretical FP usually off slightly from actual
-ions often not 100% dissociated
-formation of ion pairs (cation + anion)
=[ions] in 1.00 m NaCl > 1.00 m but < 2.00 m
=number of particles is less in a solution
The more diluted a solution is, the less likely to form an ion pair,
the less difference between the theoretical and actual FPs
The van’t Hoff factor (i) accounts for effects of dissociation
Actual conc of particles
actual number of particles in solution after dissociation
i=
number of formulas units initially dissolved in solution
nominal conc of
substance
i = 1 for nonelectrolyte
∆Tf = Kf(im) ∆Tb = Kb(im) π = (iM)RT
where (im) = actual molality of particles
and (iM) = actual molarity of particles
Practice Example
What is the theoretical/expected van’t Hoff factor for magnesium
bromide?
What is the theoretical/expected van’t Hoff factor for ammonium

sulfate?
What is the theoretical/expected van’t Hoff factor for aluminum

carbonate?
Electrolyte Solutions (5)
Concentration has an effect on experimentally measured van’t Hoff

factors (i).
The more diluted a solution is, the less likely to form an ion pair,
the less difference between the theoretical and actual van’t Hoff
factors (i).
Worked Example 13.7
The osmotic pressure of a 0.0100 M potassium iodide (KI) solution at 25°C is
0.465 atm. Determine the experiment van’t Hoff factor for KI at this concentration.
actual number of particles in solution after dissociation Look for this
i=
number of formulas units initially dissolved in solution
0.0100 M KI
Use osmotic pressure to calculate the actual molar concentration of KI, and
divide by the nominal concentration of 0.01000 M to determine i.
R = 0.08206 L∙atm/K∙mol, and T = 298 K.
Solution Solving π = MRT for M,
M = π/RT = (0.465 atm)/(0.08206 L∙atm/K∙mol)(298 K) = 0.0190 M
i = (0.0190 M)/(0.0100 M) = 1.90
The experimental van’t Hoff factor for KI at this concentration is 1.90.

Worked Example 13.7
The osmotic pressure of a 0.0100 M potassium iodide (KI) solution at 25°C is
0.465 atm. Determine the experiment van’t Hoff factor for KI at this concentration.
Solution Solving π = iMRT for i,
i = π/(MRT) = (0.465 atm)/[(0.0100 M)(0.08206 L∙atm/K∙mol)(298 K)]

= 1.90
The experimental van’t Hoff factor for KI at this concentration is 1.90.

Practice Example
The freezing-point depression of a 0.100 m MgSO4 solution is
0.225 ℃. Determine the experimental van’t Hoff factor of MgSO4
at this concentration.
Solution Solving ∆Tf = Kf(im) for i,
i = ∆Tf /(mKf)= (0.225 ℃)/[(0.100 m)(1.86 ℃/m)]
i = 1.21
The experimental van’t Hoff factor for MgSO4 at this concentration is 1.21.
Chemistry: Atoms First
Fourth Edition
Julia Burdge and Jason Overby
Chapter 14
Chemical Kinetics
© 2021 McGraw Hill. All rights reserved. Authorized only for instructor use in the classroom. No reproduction or
further distribution permitted without the prior written consent of McGraw Hill.
14.1 Reaction Rates
Reactions occur at different speeds

-Some happen almost instantaneously
=photosynthesis
=ignition of gasoline
-Some others can take millions of years
=hardening of cement
=conversion of diamond to graphite
Chemical kinetics is the study of how fast reactions take place
Speed of a reaction → reaction rate

14.1 Reaction Rates
Why reaction rate is important to study?

-Speed up desirable reactions
-Minimize damage by undesirable reactions
-Useful in: = drug design and treating diseases
= pollution control
= food processing
= industrial processes
14.2 Collision Theory of Chemical Reactions
• Given the following: reactants → products

• Most reactions occur thru collisions between reactants
-vast majority of collisions involve 2 particles ONLY
• The reaction rate is proportional to the number of effective
collisions per second
-effective collision → one that yields product
#number
of effective collisions
of collisions
rate 
s
• Anything that increases the frequency of collisions will increase
the rate
-increase concentration of reactants
-increase surface area
Only a small fraction of all collisions are effective
1. Molecular Kinetic Energy:

- molecules have kinetic energy (motion)
= the faster they move, the more kinetic energy
- in a collision,
= kinetic energy transferred into vibrational energy
(internal motion)
- if vibrations large enough, bonds can break
= 1st step to forming products
- a minimum combined energy required to initiate reaction
= Activation Energy (Ea)
- if less than Ea, then ineffective collision and reactants bounce
off each other unchanged
Potential Energy Diagram
Effective collision generates an activated complex, also called
transition state—temporary species
Potential Energy diagram
Transition state
reactants
Products
Effective: adequate kinetic energy in collision (>Ea)
Ineffective: inadequate kinetic energy in collision (<Ea)

2. Also require correct Molecular Orientation
- molecules need to be oriented properly with respect to each
other, or else collision will be ineffective
= correct bonds must break/form between correct atoms
Cl + NOCl → Cl2 + NO
Effective
Ineffective
• Only a fraction of all collisions have correct orientation

• Of those, only a small fraction have enough energy to be effective
• Temperature ∝ average KE
-as temperature increases, a larger fraction of the molecules have
a sufficient energy (KE) to participate in productive collision
• Most reactions occur faster at a higher temperature
-food spoilage is faster in summer
14.3 Measuring Reaction Progress and Expressing
Reaction Rate: Average Reaction Rate
A→B
One can express rate as either:
• rate of disappearance/consumption of reactants (decrease)
• rate of appearance/production of products (increase)
Average Reaction Rate
A→B
[A] decreases
One can express rate as - D [A] or D [B] , unit is M/s

Dt Dt
-rate is positive quantity (negative in [A] expression makes rate positive)
-these are average rates over time
• Rate can be monitored through color change, conductance

change, pressure change, etc.
Br2(aq) + HCOOH(aq) → 2Br–(aq) + 2H+(aq) + CO2(g)

(Colored)
Monitor loss of color using absorbance spectroscopy

to determine the [Br2] as the reaction proceeds
Time (s) [Br2] (M)
0.0 0.0120
50.0 0.0101
100.0 0.00846
150.0 0.00710
200.0 0.00596
250.0 0.00500
300.0 0.00420
350.0 0.00353
400.0 0.00296
Average rate = –∆[Br2]/∆t = –([Br]final – [Br]initial)/(tfinal – tinitial)

Calculate the average rate over the first 150 seconds of the reaction:
Average rate = –∆[Br2]/∆t = –(0.00710 M– 0.0120 M)/(150 s) = 3.27×10-5 M/s
Calculate the average rate over the next 150 seconds of the reaction:
Average rate = –∆[Br2]/∆t = –(0.00420 M– 0.00710 M)/(150 s) = 1.93×10-5 M/s
Average rate changes with time
• [Br2] decreases, less reactant molecules, less effective collisions
• Plot of [Br2] vs time = curve (not linear)
Instantaneous Rate
The instantaneous rate is the rate at a specific instance in time
-slope of a tangent to the curve
-more useful than average rate
-will use instantaneous rate from now on (unless otherwise indicated)
-instantaneous rate (slope) decreases over time
Instantaneous Rate
Instantaneous rate (slope) decreases over time
- because [Br2] decreases over time (less effective collisions)
When [Br2] is halved; the rate is halved

• Rate is proportional to [Br2]
Rate ∝ [Br2] Rate = k [Br2], k is rate constant
Rate law
Instantaneous Rate
k is constant as long as temp is constant (temp dependent)
Rate = k [Br2], rearrange to get k = rate/[Br2]
Calculate rate constant k using data in Table below:
at t = 50.0 s: k = (3.52 × 10-5 M/s) / (0.0101 M) = 3.49 × 10-3 s-1
at t = 300 s: k = (1.48 × 10-5 M/s) / (0.00420 M) = 3.52 × 10-3 s-1
Note: small difference is due to experimental variation
Time (s) [Br2] (M) Rate (M/s)
0.0 0.0120 4.20 × 10−5
50.0 0.0101 3.52 × 10−5
100.0 0.00846 2.96 × 10−5
150.0 0.00710 2.49 × 10−5
200.0 0.00596 2.09 × 10−5
250.0 0.00500 1.75 × 10−5
300.0 0.00420 1.48 × 10−5
350.0 0.00353 1.23 × 10−5
400.0 0.00296 1.04 × 10−5
Stoichiometry and Reaction Rate
When stoichiometric ratios are not 1:1:

A → 2B
Δ[A] is half as Δ[B]
1
rate = –∆[A]/∆t = ×(∆[B])/∆t
2
In general:
aA + bB → cC + dD
1 D [A] 1 D [B] 1 D [C] 1 D [D]
rate = - =- = =
a Dt b Dt c Dt d Dt
Stoichiometry and Reaction Rate (2)
Write the rate expressions for the following reaction:
CO2(g) + 2H2O(g) → CH4(g) + 2O2(g)
Solution:
Use the equation below to write the rate expressions.
1 D [A] 1 D [B] 1 D [C] 1 D [D]

rate = - =- = =
a Dt b Dt c Dt d Dt
rate = –∆[CO2]/∆t = –(1/2)∆[H2O]/∆t = ∆[CH4]/∆t = (1/2)∆[O2]/∆t
Worked Example 14.2
Consider the reaction
4NO2(g) + O2(g) → 2N2O5(g)
At a particular time during the reaction, nitrogen dioxide is being consumed at the
rate 0.00130 M/s. (a) At what rate is molecular oxygen being consumed? (b) At
what rate is dinitrogen pentoxide being produced?
Strategy Determine the rate of reaction and, using the stoichiometry of the
reaction, convert to rates of change for the specified individual species.
Solution
rate = −(1/4)Δ[NO2]/Δt = −Δ[O2]/Δt = (1/2)Δ[N2O5]/Δt
We are given
Δ[NO2]/Δt = −0.00130 M/s
where the minus sign indicates that the concentration of NO2 is decreasing with
time.
4NO2(g) + O2(g) → 2N2O5(g)
Solution The rate of reaction, therefore, is
rate = −(1/4)Δ[NO2]/Δt = −(1/4)(−0.00130 M/s)
= 3.25×10−4 M/s
(a) rate = 3.25×10−4 M/s = −Δ[O2]/∆t
Δ[O2]/∆t = −3.25×10−4 M/s
Molecular oxygen is being consumed at a rate of 3.25×10−4 M/s.
(b) rate = 3.25×10−4 M/s = (1/2)Δ[N2O5]/Δt
2(3.25×10−4 M/s) = Δ[N2O5]/Δt
Δ[N2O5]/Δt = 6.50×10−4 M/s
Dinitrogen pentoxide is being produced at a rate of 6.50×10−4 M/s.

14.4 Dependence of Reaction Rate on Reactant
Concentration: The Rate Law
In general: aA + bB → cC + dD
-The rate law is an equation that relates the rate of reaction to

the concentrations of reactants
rate = k[A]x[B]y
-k: the rate constant
-x and y: exponents = order of the reaction with respect to each
reactant
= exponents can only be determined experimentally for
overall reaction
=THEY ARE NOT EQUAL TO COEFFICIENTS FROM
BALANCED CHEMICAL REACTION!
14.4 Dependence of Reaction Rate on Reactant
Concentration: The Rate Law
Order of the reaction with respect to each reactant
- 1st order – rate directly proportional to [A]: Rate = k [A]1= k [A]
- 2nd order – rate proportional to [A]2: Rate = k [A]2
- 0th order – independent of [A]: Rate = k [A]0 = k
- Sum of all exponents (order) indicates the overall reaction order
In case of Br2(aq) + HCOOH(aq) → 2Br–(aq) + 2H+(aq) + CO2(g)

rate = k [Br2]x [HCOOH]y
x = 1; y = 0 [first order with respect to Br2; zeroth order with

respect to HCOOH]
x + y = 1 + 0 =overall reaction order = 1
Experimental Determination of the Rate Law
Commonly determined by looking at initial rates

-The initial rate: instantaneous rate at the beginning of reaction.
For the following reaction

F2(g) + 2ClO2(g) → 2FClO2(g)
Initial Rate Data for the Reaction between F2 and ClO2

Experiment [F2](M) [ClO2](M) Initial Rate (M/s)
1 0.10 0.010 1.2 x 10–3
2 0.10 0.040 4.8 x 10–3
3 0.20 0.010 2.4 x 10–3

F2(g) + 2ClO2(g) → 2FClO2(g) rate = k[F2]x[ClO2]y
1 0.10 0.010 1.2 x 10–3

[F2] [ClO2] Rate
2 0.10 0.040 4.8 x 10–3
doubles constant doubles
3 0.20 0.010 2.4 x 10–3
2 = 2x → x = 1
The reaction is first order in F2: x = 1 rate = k[F2]1[ClO2]y
F2(g) + 2ClO2(g) → 2FClO2(g) rate = k[F2][ClO2]y
1 0.10 0.010 1.2 x 10–3

[F2] [ClO2] Rate
constant x4 x4
2 0.10 0.040 4.8 x 10–3
3 0.20 0.010 2.4 x 10–3
4 = 4y → y = 1
The reaction is first order in ClO2; y = 1 rate = k[F2]1[ClO2]1
Over reaction order = 2
F2(g) + 2ClO2(g) → 2FClO2(g) rate = k[F2][ClO2]
Once the order for each reactant is known, pick any set of data to
determine the rate constant, k
1 0.10 0.010 1.2 x 10–3
2 0.10 0.040 4.8 x 10–3
3 0.20 0.010 2.4 x 10–3
Determine k by substituting info from any single experiment:
rate = 1.2[F2][ClO2]
For the reaction: 3 A(g) + 2 B(g) → 2 C(g) + 2 D(g)
The following data were collected at constant temperature. Determine the rate law
for this reaction.
Trial Initial [A] (M) Initial [B] (M) Initial Rate (M min–1)
1 0.200 0.100 6.00 × 10–2
2 0.100 0.100 1.50 × 10–2
3 0.200 0.200 1.20 × 10–1
4 0.300 0.200 2.70 × 10–1
Rate Constant Unit v.s. Overall Order of Reaction
The units of a rate constant (k) depend on the overall order of rxn
Items of note:
1. unit of rate is always M s–1 (unless told otherwise)
2. rate law usually defined in terms of reactants only
3. exponents usually positive whole numbers or zero
- can be negative (not seen too often): inhibitor
- can also be fraction/decimal value (you won’t see)
Rate Constant Unit v.s. Overall Order of Reaction
The units of a rate constant (k) depend on the overall order of rxn
-can figure out unit of k from overall order, and vice versa
rate = k[A]x[B]y
What’s the unit of k if the overall reaction order is 4?
x+y=4 [A]x[B]y has a unit of M4
rate = k[A]x[B]y rate M s–1 = M–3 s–1

k=
M s–1 M4 [A]x[B]y M4
What’s the overall reaction order if unit of k is M-34∙s-1?
M s –1
rate M 35
rate = k [A]x[B]y [A]x[B]y = =
k M–34 s–1
M s–1 M–34 s–1
x + y = 35
overall reaction order is 35
14.5 Dependence of Reactant Concentration on Time
The rate law can be used to determine the rate of a reaction using the
rate constant and the reactant concentrations:
rate law
rate = k[A]x[B]y
rate rate constant
A rate law can also be used to determine the reactant concentration

at a specific time during a reaction.
-if you start with [X] = 0.100 M, how long until the [X] drops
to 0.001 M?
First-Order Reactions
A first-order reaction is a reaction whose rate depends on the

concentration of one of the reactants raised to the first power.
C2H6 → 2 ·CH3 rate = k[C2H6]
2N2O5(g) → 2NO2(g) + O2(g) rate = k[N2O5]
A+B→C rate = k[A]x[B]y rate = k[A]1[B]0

or
rate = k[A]0[B]1
In a first-order reaction of the type
A → products
The rate can be expressed as the rate of change in reactant

concentration,
rate = –∆[A]/∆t
as well as in the form of the rate law:
rate = k[A]
Setting the two expressions equal to each other yields:
rate = –∆[A]/∆t = k[A]

−𝜕 𝐴
𝑟𝑎𝑡𝑒 = =𝑘 𝐴
𝜕𝑡
1
𝜕 𝐴 = −𝑘 𝜕𝑡
𝐴
𝐴𝑡 𝑡
1
න 𝜕 𝐴 = − න 𝑘 𝜕𝑡
𝐴0 𝐴 0
ln 𝐴 𝑡 − ln 𝐴 0 = −𝑘 𝑡
ln 𝐴 𝑡 = −𝑘 𝑡 + ln 𝐴 0
𝐴 0
or ln =𝑘𝑡
𝐴 𝑡
The equation above is sometimes called the integrated rate law for a
first order reaction.
Worked Example 14.4
The decomposition of hydrogen peroxide is first order in H2O2.
2H2O2(aq) → 2H2O(l) + O2(g)
The rate constant for this reaction at 20C is 1.8×10−5 s−1. If the start
concentration of H2O2 is 0.75 M, determine (a) the concentration of H2O2
remaining after 3 h and (b) how long it will take for the H2O2 concentration to
drop to 0.10 M
Strategy (a) Use ln([A]0/[A]t) = kt to find [H2O2]t where t = 3 h, time t for part
(a) is (3 h)(60 min/h)(60 s/min) = 10,800 s.
Solution
(a) ln([H2O2]0/[H2O2]t) = kt
ln(0.75 M/[H2O2]t) = (1.8×10−5 s−1)(10,800 s) = 0.1944
Take the inverse natural logarithm of both sides of the equation to get
(0.75 M)/[H2O2]t = e0.1944 = 1.215
[H2O2]t = (0.75 M)/(1.215) = 0.62 M
The concentration of H2O2 after 3 h is 0.62 M.

Strategy (b) Use ln([A]0/[A]t) = kt to solve for t to determine how much time
must pass for [H2O2]t to equal 0.10 M. [H2O2]0 = 0.75 M.
Solution
(b) ln[(0.75 M)/(0.10 M)] = 2.015 = (1.8 × 10−5 s−1)t
2.015/(1.8×10−5 s−1) = t = 1.12 × 105 s
The time required for the peroxide concentration to drop to 0.10 M is 1.1×105 s
or about 31 h.
ln([A]0/[A]t)= kt
ln[A]t = –kt + ln[A]0

y m y-intercept
Rearrangement in this way has the form of the linear
equation y = mx + b.
Slope = –k (can determine rate

constant graphically)
Intercept = ln[A]0
Second-Order Reactions
A second-order reaction is a reaction whose rate depends on the
concentration of one reactant raised to the second power or on the
product of the concentrations of two different reactants (first order in
each).
𝑟𝑎𝑡𝑒 = 𝑘 𝐴 2 𝑟𝑎𝑡𝑒 = 𝑘 𝐴 𝐵
We focus on this type
A → products
−𝜕 𝐴 2
𝑟𝑎𝑡𝑒 = =𝑘 𝐴
𝜕𝑡
Similar math we
did for first order
1/[A]t = kt + 1/[A]0
integrated rate law for a second
order reaction
y = mx + b
Worked Example 14.7
Iodine atoms combine to form molecular iodine in the gas phase:
I(g) + I(g) → I2(g)
This reaction is second order and has a rate constant of 7.0×109 M−1∙s−1 at 23°C.
If the initial concentration of I is 0.086 M, calculate the concentration after 2.0
min.
Strategy Use 1/[A]t = kt + 1/[A]0 to determine [I]t at t = 2.0 min;
Solution t = (2.0 min)(60 s/min) = 120 s
1/[A]t = kt + 1/[A]0
= (7.0×109 M−1∙s−1)(120 s) + 1/(0.086 M)
= 8.4×1011 M−1
[A]t = 1/(8.4×1011 M−1) = 1.2×10−12 M
The concentration of atomic iodine after 2 min is 1.2×10−12 M.

Zero Order Reactions
Reaction whose rate is independent of reactant concentration
A → products
𝑟𝑎𝑡𝑒 = 𝑘 𝐴 0 = 𝑘
The rate of a zero-order reaction is a constant.
[A]t = – k t + [A]0
integrated rate law for a zero order reaction
y = mx + b
Summary
One can graphically determine the reaction order once the [A] and
time data is collected
Pay attention to the y-axis and the y-intercept on these plots in order
to figure out the order graphically
Consider the reaction: A→B
for which k = 5.78 × 10–4 s–1 at 110 ℃. How much time is required for this reaction
to be 75% complete?
This reaction is 1st order reaction
If reaction is 75% complete, it means 25% of the original reactant left
Then [A]t/[A]0 = 25% = 0.25
ln([A]0/[A]t)= kt or ln[A]t = –kt + ln[A]0
[A]0/[A]t = 1/0.25 = 4
ln(4) = 5.78 × 10–4 s–1 × t
t = ln(4)/(5.78 ×10–4 s–1)
t = 2.40 ×103 s
for which k = 5.78 × 10–4 s–1 at 110 ℃. How much time is required for [A]0 to
decrease to 25%?
This reaction is 1st order reaction
Decrease to 25% means 25% of the original reactant left
Then [A]t/[A]0 = 0.25
ln([A]0/[A]t)= kt or ln[A]t = –kt + ln[A]0
[A]0/[A]t = 1/0.25 = 4
ln(4) = 5.78 × 10–4 s–1 × t
t = ln(4) /(5.78 ×10–4 s–1)
t = 2.40 ×103 s
for which k = 0.13 M-1 s–1 at 110 ℃. If the initial concentration of A is 0.065 M.
What is the concentration of A after 25 s?
This reaction is 2nd order reaction based on the unit of rate constant
We know k, t, and [A]0
1 1
= 𝑘𝑡 +
[𝐴]𝑡 [𝐴]0
1 −1 −1
1
= 0.13 𝑀 𝑠 × 25.0 𝑠 +
[𝐴]𝑡 0.065 𝑀
1
= 18.6 𝑀−1
[𝐴]𝑡
[𝐴]𝑡 = 0.0537 𝑀
for which k = 0.13 M-1 s–1 at 110 ℃. If the concentration of A dropped to 0.065 M in
89.0 s after the reaction was started. What was the concentration of A for this
reaction to begin with?
This reaction is 2nd order reaction based on the unit of rate constant
We know k, t, and [A]t, solve for [A]0
1 1
= 𝑘𝑡 +
[𝐴]𝑡 [𝐴]0
1 −1 −1
1
= 0.13 𝑀 𝑠 × 89.0 𝑠 +
0.065 𝑀 [𝐴]0
[𝐴]0 = 0.26 𝑀
Worked Example
Consider the first order reaction: 3A→2B
for which k = 7.5×10-3 s-1 at 110 ℃. With a starting concentration of [A] = 2.25 M,
what will [A]t be after 2.0 minutes?
Answer: [A]t will be 0.915 M after 2.0 min

Half-life of Reaction
The half-life (t1/2) is the time required for half of the reactant to
disappear (i.e. time it takes for the reactant concentration to drop to half
of its original value)
First order reaction
You can derive 𝑘 from 𝑡1Τ2 , and vice versa

Worked Example
The decomposition of H2O2 is first order:
H2 O2 → H 2 O + ½ O2
At a particular temperature, the rate constant = 7.00 × 10–4 s–1 and [H2O2]0 = 0.100 M.
(a) Calculate t1/2:
t1/2 = ln(2)/k = 0.693/k = 0.693/(7.00 × 10–4 s–1) = 990 s
(b) How long will it take for [H2O2]t = 0.0370 M?
ln ([A]0/[A]t) = kt
ln ([0.100 M/0.0370 M) = (7.00 × 10–4 s–1) t
0.994 = (7.00 × 10–4 s–1) t
t = 0.994/(7.00 × 10–4 s–1) = 1420 s
Worked Example
All radioactive decay reactions are 1st order reactions. For example the decay of 131I
has a half life of 8.00 days. What fraction of the original 131I is left after 24 days?
t1/2 = ln(2)/k = 0.693/k = 8.00 days
k = 0.693/(8.00 days) = 0.0866 day–1

Now we know k and we can use it to determine the
concentration or concentration fraction at 24 days
ln([A]0/[A]t) = kt
ln([A]0/[A]t) = (0.0866 day–1)(24 days) = 2.08
[A]0/[A]t = e2.08 = 8.00 ⟵This is original amount over remained amount

[A]t/[A]0 = 1/8.00 = 0.125 or 12.5% of the original 131I is left after 24 days
↑
This is fraction left after 24 days(remained amount over original amount)
Second order reaction
Larger [A]0, shorter the half-life;

Smaller [A]0, longer the half-life
Zero order reaction
Larger [A]0, longer the half-life;

Smaller [A]0, shorter the half-life
Worked Example
The second-order rate constant for the following gas-phase reaction is 0.0442 M–1 s–1:
2 C2F4(g) → C4F8(g)
We start with 0.135 mol C2F4 in a 2.00 L container, with no C4F8 initially present.
(a) What will be the concentration of C2F4 after 1.00 hr?
(b) What is the half-life of the reaction when [C2F4]0 = 0.0675 M?
(c) How long will it take for ½ of the C2F4 that remains after 1.00 hr to disappear
Worked Example
2 C2F4(g) → C4F8(g)
(a) What will be the concentration of C2F4 after 1.00 hr?
1/[A]t = kt + 1/[A]0 [A]0 = 0.135 mol/2 L=0.0675 M, 1 h = 3600 s

1/[A]t = (0.0442 M–1 s–1)(3600 s) + 1/(0.0675 M)
1/[A]t = 159.12 + 14.81 =174 M–1
[A]t = 1/(174 M–1) = 5.74 × 10-3 M
Worked Example
2 C2F4(g) → C4F8(g)
(a) What will be the concentration of C2F4 after 1.00 hr? 5.74 × 10-3 M
(b) What is the half-life of the reaction when [C2F4]0 = 0.0675 M?
t1/2 = 1/(k[A]0)
t1/2 = 1/(0.0442 M–1 s–1 × 0.0675 M)

= 335 s
Worked Example
2 C2F4(g) → C4F8(g)
(a) What will be the concentration of C2F4 after 1.00 hr? 5.74 × 10-3 M
(b) What is the half-life of the reaction when [C2F4]0 = 0.0675 M? 335 s
(c) How long will it take for ½ of the C2F4 that remains after 1.00 hr to disappear
t1/2 = 1/(k[A]0)
t1/2 = 1/(0.0442 M–1 s–1 × 5.74 × 10-3 M)

= 3942 s
= 3.94 × 103 s = 3940 s

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In Class Review Feb - 9 Lecture - 10

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Chapter 13

Physical Properties of Solutions

Solutions can be classified by the amount of solute dissolved.

An unsaturated solution can dissolve more solute at a specific

Solubility: amount (mass) of solute that forms saturated solution

How is a solution formed?

Solid solute Liquid solvent Liquid solution

1) disruption of solute-solute interactions (like breaking a bond)

ΔHsoln > 0 (endothermic) if ΔH3 < ΔH1 + ΔH2

• Solubility of solute in a solvent can be predicted:

Ionic bond > hydrogen-bond > dipole-dipole > dispersion force

Ionic F-H F-H Polar Non-polar

• Two liquids that are soluble in each other in all proportions

• Ions readily dissolve in polar solvent due to solvation by the

Which of the following dissolves best in water?

Predict whether Vitamin B6 is water soluble or fat soluble:

The amount(moles/grams) of solute relative to the amount

Mole fraction: the ratio of the number of moles of one component

mole percent = (mole fraction) x 100

Molality (m) is the number of moles of solute dissolved in 1 kg (1000

𝑚𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑒 15.56 𝑔÷180.2 𝑔/𝑚𝑜𝑙

Strategy for solving these kind of problems:

Calculate the molality of a 10.0% aqueous NaCl solution:

Denominator Mass of solution Mass of solute Mass of solvent

𝑚𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑒 0.171 𝑚𝑜𝑙 𝑁𝑎𝐶𝑙

If molality of NaCl is 1.90 m, can you determine % for NaCl

If molarity of a HCl solution is 11.8 M, can you determine %

Assume there is a total of 100 mols of the substance

Assume there is a total of 100 mols of the substance

• Solubility of solids may increase, decrease or remain relatively

Temperature effect due to heat of solution (and other factors):

gas + solvent ⇄ solution

c molar concentration of the gas solute in the solution (mol/L)

Colligative properties are properties that depend on the number of

Colligative properties we focus are:

➢ boiling point elevation

➢ freezing point depression

-solute blocks surface sites

Mole fraction: the ratio of the number of moles of one component

No solvent Pure solvent

If both solute and solvent of a

Which liquid is more volatile?

Psolution = 𝟎. 𝟒𝟒 × 𝟖𝟏 + (𝟏 − 𝟎. 𝟒𝟒) × 𝟏𝟖𝟒. 𝟓

Ans: 139 torr

Can calculate change in FP (ΔTf) or BP (ΔTb):

NOTE: Kf and m are positive numbers, which means ΔTf or ΔTb

Kf and Kb values will be provided in exams

∆Tb = Tb – Tb° (b) ΔTb = Kbm = (0.52°C/m)(5.32 m) = 2.8°C

Solution mass of ethanol = 50.0 mL × 0.789 g/mL = 39.5 g or 3.95×10−2

Solving ΔTf = Kfm for molal concentration

m = ΔTf/Kf = (1.55C)/(1.99C/m) = 0.779 m

[(0.779 mol quinine)/(kg ethanol)](3.95×10-2 kg ethanol) = 0.0308 mol quinine

molar mass of quinine = (10.0 g quinine)/(0.0308 mol quinine) = 325 g/mol

Osmosis is the selective passage of solvent

-start with solvent on left, solution on right

Osmotic pressure (π) of a solution is the pressure required to stop

1. Use π = MRT to calculate the molarity of the solution.

π = 14.3 mmHg/(760 mmHg/atm) = 1.88×10−2 atm