Important topics for Chapter 12: Solutions and 13: Kinetics  Batamo

Chapter 12
1. Solubility:
a. Temperature: solubility increases with increasing temp for all compounds, except for some ionic
compounds (Ce2(SO4)3).
b. Pressure: only affects gases. Solubility increases with increasing pressure. (Henry’s law).
c. Molar mass: solubility increases with increasing molar mass. This is especially true for gases.
d. ****“Like dissolves like” rule: that is, polar compounds dissolve in polar solvents; non-polar
compounds dissolve in non-polar solvents.
2. Concentrations:
a. w % (percent by mass) = (mass of solute/mass of solution) x 100%
b. w/v % (percent by volume) = (mass of solute/volume of solution, mL) x 100% c. ppm & ppb
d. molality (m) = mole of solute/ kg of solvent e. molarity (M) = mole of solute/ L of solution

3. ****Colligative properties:
a. Lowering vapor pressure in solution (Raoult’s law) P = Psolvent – Psolution = Psolvent x Xsolute x i (i.e. vapor
pressure of solution < the pure solvent).
b. * Freezing point depression: Tf = Kf x m x i (i.e. the freezing point of solution < the pure solvent)
c. *Boiling point elvation: Tb = Kb x m x i (i.e. the boiling point of solution > the pure solvent)
d. Osmotic pressure:  = iMRT (i.e. the flow of solvent is from a higher concentrated solution to a lower
concentrated solution)
Note: from colligative properties, especially b, c, and d, one can calculate the molar mass of unknown
compounds and also predict the freezing point and boiling point of a solution.

Note that i is the van Hoff’s factor or say the factor that corrects for the number of moles of particles per
mole of solute. In a dilute solution, the van Hoff’s constant usually equals to the sum of coefficients of
products in a net-ionic equation. As for a concentrated solution, van Hoff’s constant is usually smaller than
the sum of coefficients of products in a net-ion equation. This is due to the fact that the ion pairs will form
during a concentrated solution.

For example,
i = 1 for nonelectrolytes like glucose because it does not form ions in solutions.
i = 2 for NaCl, KOH, KNO3, etc. because they are soluble strong electrolytes that do form ions in
aqueous solutions.
i = 3 for CaCl2, Ba(OH)2, Na2SO4, etc. because they are soluble strong electrolytes that do form ions in
aqueous solutions.
i = 4 for AlCl3, etc. because it is a soluble strong electrolyte that does form ions in aqueous solutions.

1 < i < x+y for soluble weak electrolytes, MxWy. For example, i is between 1 and 2 for CH3COOH
because it dissociates about 1-3% into CH3COO- and H+ ions in aqueous solutions.

Chapter 13
1. *Definition: consideration of the correlation of rates and coefficients among each reactant and product
for a general reaction as a A + b B  c C + d D
Rate = -(1/a)([A]/t) = -(1/b)([B]/t) = +(1/c)([C]/t) = +(1/d)([D]/t)
Note: Rate is defined as a positive value. For reactants A and B, the values of [A]/t and [B]/t are both
negative; however, for the products C and D, the values of [C]/t and [D]/t are both positive.

2.***Rate Law: relates to reactant(s) only. For a general reaction as

aA+bBcC+dD Rate = k[A]x[B]y
Note: (1) x and y may NOT be identical to the coefficients a and b. The values of x and y can be ANY
number, including zero or positive or negative integers or fractions. (2) Rate law MUST be determined
from experiments; it has NOTHING to do with the overall balanced equation. (3) x is the reaction order for
reactant A, y is the reaction order for B, and x+y is the overall reaction order.

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3.**For first order reaction, a A : Rate law, R, = k[A], k: rate constant, unit: s-1
Relation between concentration and time: ln([A]o/[A]t) = kt; half-life is t1/2 = ln2/k = 0.693/k
Relation between temperature and rate constants: ln(k2/k1) = (-Ea/R) x (1/T2 –1/T1); R = 8.314 J/mol.K

4. For second order reaction, a A : Rate law, R, = k[A]2; k: rate constant; unit: s-1M-1.
Relation between concentration and time: 1/[A]t - 1/[A]o = kt; half-life is t1/2 = 1/k[A]o

5. Collision model for reaction rate: terminology includes molecular orientation, activation energy (Ea),
transition state (or activated complex), and intermediate. Note that temperature affects both k (rate
constant) and K (equilibrium constant) but not Ea. However, catalyst can affect k only by providing a
different reaction pathway with much lower activation energy.

6.***Reaction mechanism: given a proposed mechanism identify the rate-determining step, intermediate(s),
catalyst(s), reaction order to each reactant and overall reaction order. Watch for the mechanism involves
intermediate(s). Note that the intermediate(s) and catalyst(s) doe not show up in the overall reaction. How
to differentiate the intermediate(s) and catalyst(s)? The intermediate must be generated first and then be
consumed; while the catalyst must be consumed first and then re-generated.

Practice for Exam I (There are 25 multiple choice questions in Exam I: chap 12 & 13)
Keys are shown in bold.

1. Which of the following concentration unit will be affected by temperature?

(a) mass percent (b) mole fraction (c) molarity (d) molality (e) ppm

2. Which of the following action will reduce the solubility of a gas in water?
(a) pressure (b) temperature (c) molar mass of the gas (d) acidic or basic gas

3. A 0.270 M KOH solution has a density of 1.01 g/mL. Calculate the molality (m) of KOH.
(a) 0.271 (b) 0.273 (c) 0.265 (d) 0.267

4. There are four aqueous solutions: 0.5 m NaI, 0.5 m C6H12O6, 0.5 m K2SO4, and 0.5 m CH3COOH.
Arrange the order of boiling points and freezing point in an increasing order for the above aqueous
solutions.
Increasing order of boiling point: 0.5 m C6H12O6 < 0.5 m CH3COOH < 0.5 m NaI < 0.5 m K2SO4.
Increasing order of freezing point: 0.5 m K2SO4 < 0.5 m NaI < 0.5 m CH3COOH < 0.5 m C6H12O6.

5. A solution of 12.00 g of an unknown nondissociating compound dissolved in 200.0 g of benzene freezes

at 3.45oC. The Kf of benzene is 5.07oC/m. The freezing point of benzene is 5.45oC.
(a) What is the mass percent of the solution? 5.66%
(b) What is the molality of the unknown solution? 0.394 m
(c) How many moles of unknown in the solution? 0.0789 mol
(d) What is the molar mass of the unknown? 152.09 grams
(e) Assume the density of the unknown solution is 1.35 g/mL, what is the molarity of the unknown
solution? 0.502 M

6. Which of the following pair is miscible (i.e. soluble to each other)?

(a) CH3OH and C6H6 (b) CCl4 and H2O (c) C6H12O6 and C2H5OH (d) CH3Cl and CH3COOH

7. What’s the concentration if the osmotic pressure for sucrose, C12H22O11, solution is 0.048 atm at 20oC?
0.002 M

8. Given the following data for the reaction 2A + B + C  D + E

Experiment Initial [A] Initial [B] Initial [C] Initial Rate of Formation of E
1 0.20 M 0.20 M 0.20 M 2.4 x 10-6 M.min-1
2 0.40 M 0.30 M 0.20 M 9.6 x 10-6 M.min-1
3 0.20 M 0.30 M 0.20 M 2.4 x 10-6 M.min-1

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 4 0.20 M 0.40 M 0.60 M 7.6 x 10-6 M.min-1

(a) What is the reaction order for A, B, C respectively and the overall reaction order?
(b) Using the data from experiment 2, what is the rate constant?
(a) The reaction order for A is second order, for B is zero order, and for C is first order.
(b) k = 3 x 10-4 M-2.min-1

9. The following mechanism for the reaction between H2 and CO to form formaldehyde, H2CO, has been
proposed: Step 1 H2  2H (fast, equilibrium)
Step 2 H + CO  HCO (slow)
Step 3 H + HCO  H2CO (fast)
(a) Which step is the rate-determining step? Step 2
(b) Write the balanced equation for the overall reaction. H2 + CO  H2CO
(c) Identify any intermediates in this proposed mechanism. H and HCO
(d) What is the overall reaction order? Note: Intermediate(s) must be excluded in the rate law. 3/2

10. The reaction 2N2O5(g)  2N2O4(g) + O2(g) obeys the rate law: rate = k[N2O5]. In which the specific
rate constant is 0.00840 s-1. If 2.50 moles of N2O5 were placed in a 5.0-liter container at that temperature,
how many moles of N2O5 would remain after 1.00 minute? Given the formula as ln([At]/[A0]) = -kt.
1.51 moles

11. The gas-phase decomposition of NOBr is second order in [NOBr], with k = 0.810 M-1.s-1 at 10oC. We
start with 4.00 x 10-3 M NOBr in a flask at 10oC. How many seconds does it take to use up 1.50 x 10-3 M of
this NOBr? Given the formula for second order reaction as 1/[A]t = kt + 1/[A]o
185.19 seconds

12. The gas-phase decomposition of ethyl iodide to give ethylene and hydrogen iodide is a first-order
reaction. C2H5I  C2H4 + HI
At 600 K, the value of k is 1.60 x 10-5 s-1. When the temperature is raised to 700 K, the value of k increases
to 6.36 x 10-3 s-1. What is the activation energy for this reaction?
Given the formula as ln(k2/k1) = (-Ea/R) x (1/T2 –1/T1) where R = 8.314 J/mol.K. Please note that this
formula is same as the ones provided in the textbook, p. 573, if you understand the mathematical meaning
of logarithms.
209.1 kJ.

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Detailed Answers for Practice for Exam I (Chap 12 & 13)

Chap 12
1. (c) molarity.
Hint: Examine the definition or formula of concentration unit. As volume is affected by temperature, the
concentration unit that involves volume will be affected by temperature.

2. (b) temperature.
Hint: The solubility of gas in water involves several factors: temperature (p. 512), pressure (p.p. 513-514),
polarity and/or acidity/basicity (p.p. 457-458) of the gas. Please note: hydrogen floride, HF(g), dissolving
in water turns to be hydrofloric acid, HF(l); Increasing pressure of pressure applying on a gas increases
the solubility of gas. Increasing temperature decreases solubility. Any gas whether it is acidic or basic is
polar and thus is very soluble in water.

3. (a) 0.271.
Hint: See Example 12.4, p. 510. Or consider the formula of molality (m) = mole of solute/ kg of solvent
and the formula of molarity (M) = mole of solute/ Liter of solution. Since the M and density are given, we
can simply assume 0.270 M KOH solution contains 0.270 mole KOH and the volume of solution is one
liter. Therefore, the mass of solution = (1.01 g/mL) x (1000 mL/L) = 1010 grams.
Thus, mass of solvent = mass of solution – mass of solute = 1010 - 0.270x56.1 = 994.85 grams = 0.99485
kg. Therefore, m = 0.270/0.99485 = 0.271. Please note that when the solution is very dilute, its m is very
close to M.

4. Increasing order of boiling point: 0.5 m C6H12O6 < 0.5 m CH3COOH < 0.5 m NaI < 0.5 m K2SO4.
Increasing order of freezing point: 0.5 m K2SO4 < 0.5 m NaI < 0.5 m CH3COOH < 0.5 m C6H12O6.
Hint: See Example 12.8, p. 522 (non-electrolyte) and p. 528 (electrolyte) formulas to figure out ΔT and
then figure out Tb and Tf for solutions. By applying (12.10) and (12.11) where i is the van Hoff’s factor or
constant, i = 1 for non-electrolyte; 1 < i < x+y for weak electrolyte; and i = x+y for strong electrolyte. Note
that x+y is the sum of coefficients from the products in a net-ionic equation, or say the sum of subscripts
for a compound MxNy or Ax(DE)y or (AE)x(GJ)y or (AE)xGy.

5. (a) What is the mass percent of the solution? (b) What is the molality of the unknown solution? (c) How
many moles of unknown in the solution? (d) What is the molar mass of the unknown? (e) Assume the
density of the unknown solution is 1.35 g/mL, what is the molarity of the unknown solution?
(a) mass % = (mass of solute / mass of solution) x 100% = 12/(12+200) x 100% = 5.66%
(b) See example 12.10, p. 526. Or by applying (12.11) to calculate m. Please note that benzene is a non-
electrolyte and its i = 1. Thus ΔTf = Tf, solvent – Tf, solution = 5.45 – 3.45 = 2.00.
Since ΔTf = i x Kf x m, the m = ΔTf /(i x Kf ) = 2.00/(1x5.07) = 0.394.
(c) As m = mole solute /kg solvent, the mole solute = m x kg solvent = 0.394 x 0.2000 = 0.0789.
(d) Molar mass of solute (i.e. unknown) = mass / mole = 12.00 / 0.0789 = 152.09 grams.
(e) Volume of solution = mass of solution /density of solution = (12.00+200.0)/1.35 = 157.04 mL. Thus,
M = mole solute/ Liter solution = 0.0789/0.15704 = 0.502.

6. (c) C6H12O6 and C2H5OH.

Hint: Like dissolves like rule: polar substance dissolves in polar solvent; non-ploar dissolves in non-polar.

7. 0.002 M.
Hint: Apply the formula (12.12). Please note that sucrose, C12H22O11, is a non-electrolyte.
According to Π = iMRT leading to M = Π/iRT = 0.048/1x0.082x(273.15+20) = and thus M = 0.002.

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Chap 13
8. Hint: Example 13.3, p. 555.
(a) Apply R = k[A]x[B]y[C]z to figure out the reaction orders for A, B and C respectively. Compare
experiments 1 and 3 to figure out the reaction order, y, for B, which leads to y = 0, zero order. Compare
experiments 2 and 3 to figure out the reaction order, x, for A, which leads to x = 2, second order. Compare
experiments 1 and 4 to figure out the reaction order, z, for C, which leads to z = 1.
(b) 9.6 x 10-6 M.min-1 = k[0.40M]2[0.30M]0[0.20M]1 and thus k = 3 x 10-4 M-2.min-1

9. Hint: p.p. 575-579.

(a) The slowest step is the rate determining step. If equilibrium involves in the mechanism, it is the step
right after the equilibrium, which is step 2.
(b) The sum of all elementary steps in a mechanism is the overall reaction. Thus, it is H2 + CO  H2CO
(c) Intermediates are the ones produced as products and are consumed in the following reactions.
Intermediates can not appear in the overall reaction. Thus, they are H and HCO.
(d) R = k2[H][CO]. Because intermediates can not appear in the rate law, we have to replace the [H] with
reactant concentration. From step 1, equilibrium, we can replace [H] with [H2]. That is Rforward = Rreverse,
which k1[H2] = k-1[H]2. Thus, [H] ={k1[H2] / k-1}1/2. Therefore, R = k2{k1[H2] / k-1}1/2[CO] =
k{[H2]}1/2[CO]. So, the overall reaction order is ½ + 1 = 3/2.

10. 1.51 moles.

Hint: Example 13.4. Please note that concentration can be replaced by mole, particle number, or mass as
long as the units of the denominator and numerator in the ln are the same. Thus, for simplicity, here apply
mole instead of molar concentration. ln[At/2.5] = -0.00840x(1x60). Thus At = 1.51 moles.

11. 185.19 seconds.

Hint: Example 13.7
1/(4.00 x 10-3 – 1.50 x 10-3) = 0.810x t + (1/4.00 x 10-3). Thus 400 = 0.810t + 250  t = 185.19 seconds.

12. The gas-phase decomposition of ethyl iodide to give ethylene and hydrogen iodide is a first-order
reaction. C2H5I  C2H4 + HI
At 600 K, the value of k is 1.60 x 10-5 s-1. When the temperature is raised to 700 K, the value of k increases
to 6.36 x 10-3 s-1. What is the activation energy for this reaction?
Given the formula as ln(k2/k1) = (-Ea/R) x (1/T2 –1/T1) where R = 8.314 J/mol.K
Hint: Example 13.9.
Ln(6.36 x 10-3/1.60 x 10-5) = (-Ea/8.314) x (1/700–1/600) => 5.985 = (-Ea/8.314) x (-2.381x10-4) =>
Ea = 2.091 x 105 J = 209.1 kJ.