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CHAPTER 12

PHYSICAL PROPERTIES OF
SOLUTIONS
Question 1:
➢The density of an aqueous solution containing 10.0 percent of ethanol
(C2H5OH) by mass is 0.984 g/mL.

(a) Calculate the molality of this solution.

(b) Calculate its molarity.

(c) What volume of the solution would contain 0.125 mole of ethanol?
Answer 1:
➢Assume 100.0 g of solution.
(a) The mass of ethanol in the solution is 0.100  100.0 g = 10.0 g. The mass
of the water is
100.0 g − 10.0 g = 90.0 g = 0.0900 kg. The amount of ethanol in moles is:
Answer 1:
(b) The volume of the solution is:

The amount of ethanol in moles is 0.217 mole [part (a)].

(c)
Question 2:
➢ A miner working 260 m below sea level opened a carbonated soft drink
during a lunch break. To his surprise, the soft drink tasted rather “flat.”
Shortly afterward, the miner took an elevator to the surface. During the trip
up, he could not stop belching. Why?
Answer 2:
➢According to Henry’s law, the solubility of a gas in a liquid increases as the
pressure increases (c = kP). The soft drink tastes flat at the bottom of the
mine because the carbon dioxide pressure is greater and the dissolved gas is
not released from the solution. As the miner goes up in the elevator, the
atmospheric carbon dioxide pressure decreases and dissolved gas is released
from his stomach.
Question 3:
➢ The solubility of N2 in blood at 37°C and at a partial pressure of 0.80 atm is
5.6 × 10−4 mol/L. A deep-sea diver breathes compressed air with the partial
pressure of N2 equal to 4.0 atm. Assume that the total volume of blood in the
body is 5.0 L. Calculate the amount of N2 gas released (in liters at 37°C and
1 atm) when the diver returns to the surface of the water, where the partial
pressure of N2 is 0.80 atm.
Answer 3:
Strategy: The given solubility allows us to calculate Henry's law constant (k),
which can then be used to determine the concentration of N2 at 4.0 atm. We
can then compare the solubilities of N2 in blood under normal pressure (0.80
atm) and under a greater pressure that a deep-sea diver might experience (4.0
atm) to determine the moles of N2 released when the diver returns to the
surface. From the moles of N2 released, we can calculate the volume of N2
released.
Answer 3:
Solution: First, calculate the Henry's law constant, k, using the concentration of N2 in blood at 0.80
atm.
c
k =
P

5.6  10−4 mol/L


k = = 7.0  10−4 mol/L  atm
0.80 atm

Next, we can calculate the concentration of N2 in blood at 4.0 atm using k calculated above.
c = kP

c = (7.0  10−4 mol/Latm)(4.0 atm) = 2.8  10−3 mol/L

From each of the concentrations of N2 in blood, we can calculate the number of moles of N 2 dissolved by
multiplying by the total blood volume of 5.0 L. Then, we can calculate the number of moles of N 2
released when the diver returns to the surface.

The number of moles of N2 in 5.0 L of blood at 0.80 atm is:

(5.6  10−4 mol/L )(5.0 L) = 2.8  10−3 mol

The number of moles of N2 in 5.0 L of blood at 4.0 atm is:

(2.8  10−3 mol/L)(5.0 L) = 1.4  10−2 mol

The amount of N2 released in moles when the diver returns to the surface is:

(1.4  10−2 mol) − (2.8  10−3 mol) = 1.1  10−2 mol

Finally, we can now calculate the volume of N2 released using the ideal gas equation. The total pressure
pushing on the N2 that is released is atmospheric pressure (1 atm).

The volume of N2 released is:


nRT
VN2 =
P

(1.1  10−2 mol)(273 + 37)K 0.0821 L  atm


VN2 =  = 0.28 L
(1.0 atm) mol  K
Question 4:
➢ How many grams of urea [(NH2)2CO] must be added to 450 g of water to
give a solution with a vapor pressure 2.50 mmHg less than that of pure
water at 30°C? (The vapor pressure of water at 30°C is 31.8 mmHg.)
Answer 4:

P =  urea Pwater

2.50 mmHg = Xurea(31.8 mmHg)


Xurea = 0.0786

The number of moles of water is:


1 mol H2O
nwater = 450 g H2 O  = 25.0 mol H2O
18.02 g H2 O

nurea
 urea =
nwater + nurea

nurea
0.0786 =
25.0 + nurea

nurea = 2.13 mol

60.06 g urea
mass of urea = 2.13 mol urea  = 128 g of urea
1 mol urea
Question 5:
➢An aqueous solution contains the amino acid glycine (NH2CH2COOH).
Assuming that the acid does not ionize in water, calculate the molality of the
solution if it freezes at −1.1°C.
Answer 5:
Question 6:
➢ A solution is prepared by condensing 4.00 L of a gas, measured at 27°C and
748 mmHg pressure, into 58.0 g of benzene. Calculate the freezing point of
this solution.
Answer 6:
We first find the number of moles of gas using the ideal gas equation.

 1 atm 
 748 mmHg   (4.00 L)
mol  K
=  
PV 760 mmHg
n =  = 0.160 mol
RT (27 + 273) K 0.0821 L  atm

0.160 mol
molality = = 2.76 m
0.0580 kg benzene

Tf = Kfm = (5.12C/m)(2.76 m) = 14.1C

freezing point = 5.5C − 14.1C = −8.6C


Question 7:
➢ A solution containing 0.8330 g of a polymer of unknown structure in 170.0
mL of an organic solvent was found to have an osmotic pressure of 5.20
mmHg at 25°C. Determine the molar mass of the polymer.
Answer 7:
Strategy: We are asked to calculate the molar mass of the polymer. Grams of the polymer are given in
the problem, so we need to solve for moles of polymer.

want to calculate given

grams of polymer
molar mass of polymer =
moles of polymer

need to find

From the osmotic pressure of the solution, we can calculate the molarity of the solution. Then, from the
molarity, we can determine the number of moles in 0.8330 g of the polymer. What units should we use
for  and temperature?

Solution: First, we calculate the molarity using Equation (12.8) of the text.
 = MRT
 1 atm 
 5.20 mmHg  
  760 mmHg  mol  K
M = =  = 2.80  10−4 M
RT 298 K 0.0821 L  atm

Multiplying the molarity by the volume of solution (in L) gives moles of solute (polymer).

? mol of polymer = (2.80  10−4 mol/L)(0.170 L) = 4.76  10−5 mol polymer

Lastly, dividing the mass of polymer (in g) by the moles of polymer, gives the molar mass of the
polymer.
0.8330 g polymer
molar mass of polymer = = 1.75  104 g/mol
−5
4.76  10 mol polymer
Question 8:
➢ Arrange the following aqueous solutions in order of decreasing freezing
point, and explain your reasoning: 0.50 m HCl, 0.50 m glucose,
0.50 m acetic acid
Answer 8:
The freezing point will be depressed most by the solution that contains the most
solute particles. You should try to classify each solute as a strong electrolyte, a weak
electrolyte, or a nonelectrolyte. All three solutions have the same concentration, so
comparing the solutions is straightforward. HCl is a strong electrolyte, so under ideal
conditions it will completely dissociate into two particles per molecule. The
concentration of particles will be 1.00 m. Acetic acid is a weak electrolyte, so it will
only dissociate to a small extent. The concentration of particles will be greater than
0.50 m, but less than 1.00 m. Glucose is a nonelectrolyte, so glucose molecules
remain as glucose molecules in solution. The concentration of particles will be 0.50
m. For these solutions, the order in which the freezing points become lower is:

0.50 m glucose > 0.50 m acetic acid > 0.50 m HCl

In other words, the HCl solution will have the lowest freezing point (greatest freezing
point depression).
Question 9:
➢ A 0.86 percent by mass solution of NaCl is called “physiological saline”
because its osmotic pressure is equal to that of the solution in blood cells.
Calculate the osmotic pressure of this solution at normal body temperature
(37°C). Note that the density of the saline solution is 1.005 g/mL.
Answer 9:
Strategy: We want to calculate the osmotic pressure of a NaCl solution. Since NaCl is a strong
electrolyte, i in the van't Hoff equation is 2.
 = iMRT

Since, R is a constant and T is given, we need to first solve for the molarity of the solution in order to
calculate the osmotic pressure (). If we assume a given volume of solution, we can then use the density
of the solution to determine the mass of the solution. The solution is 0.86% by mass NaCl, so we can
find grams of NaCl in the solution.

Solution: To calculate molarity, let’s assume that we have 1.000 L of solution (1.000  103 mL). We
can use the solution density as a conversion factor to calculate the mass of 1.000  103 mL of solution.
1.005 g soln
(1.000  103 mL soln)  = 1005 g of soln
1 mL soln

Since the solution is 0.86% by mass NaCl, the mass of NaCl in the solution is:
0.86%
1005 g  = 8.6 g NaCl
100%

The molarity of the solution is:


8.6 g NaCl 1 mol NaCl
 = 0.15 M
1.000 L 58.44 g NaCl

Since NaCl is a strong electrolyte, we assume that the van't Hoff factor is 2. Substituting i, M, R, and T
into the equation for osmotic pressure gives:

 0.15 mol  0.0821 L  atm 


 = iMRT = (2)    (310 K) = 7.6 atm
 L  mol  K 
Question 10:
➢ Acetic acid is a weak acid that ionizes in solution as follows:

CH3COOH(aq)⇌CH3COO−(aq)+H+(aq)

If the freezing point of a 0.106 m CH3COOH solution is −0.203°C, calculate


the percent of the acid that has undergone ionization.
Answer 10:
➢We can calculate the molality of the solution from the freezing point depression.
Tf = Kfm
0.203 = 1.86 m
The molality of the original solution was 0.106 m. Some of the solution has ionized
to H+ and CH3COO−.
CH3COOH  CH3COO− + H+
Initial 0.106 m 0 0
Change −x +x +x
Equil. 0.106 m − x x x

At equilibrium, the total concentration of species in solution is 0.109 m.


(0.106 − x) + 2x = 0.109 m
x = 0.003 m
The percentage of acid that has undergone ionization is:
CHAPTER 13
CHEMICAL KINETICS
Question 11:
➢ Write the reaction rate expressions for the following reactions in terms of
the disappearance of the reactants and the appearance of products:

(a) 2H2(g)+O2(g)→2H2O(g)

(b) 4NH3(g)+5O2(g)→4NO(g)+6H2O(g)
Answer 11:

1 [H 2 ] [O2 ] 1 [H 2O]


(a) rate = − = − =
2 t t 2 t

1 [NH3 ] 1 [O2 ] 1 [NO] 1 [H 2 O]


(b) rate = − = − = =
4 t 5 t 4 t 6 t
Question 12:
➢ Consider the reaction

N2(g)+3H2(g)→2NH3(g)

Suppose that at a particular moment during the reaction molecular hydrogen is


reacting at the rate of 0.074 M/s.

(a) At what rate is ammonia being formed?

(b) At what rate is molecular nitrogen reacting?


Answer 12:

Strategy: The rate is defined as the change in concentration of a reactant or product with time. Each
“change in concentration” term is divided by the corresponding stoichiometric coefficient. Terms
involving reactants are preceded by a minus sign.
[N 2 ] 1 [H 2 ] 1 [NH3 ]
rate = − = − =
t 3 t 2 t
Solution:
(a) If hydrogen is reacting at the rate of −0.074 M/s, the rate at which ammonia is being formed is
1 [NH3 ] 1 [H 2 ]
= −
2 t 3 t
or
[NH3 ] 2 [H 2 ]
= −
t 3 t
[NH3 ] 2
= − (−0.074 M/s) = 0.049 M/s
t 3

(b) The rate at which nitrogen is reacting must be:


[N 2 ] 1 [H 2 ] 1
= = (−0.074 M/s) = − 0.025 M/s
t 3 t 3
Question 13:
➢ Use the data in Table 13.2 to calculate the rate of the reaction at the time
when [F2] = 0.010 M and [ClO2] = 0.020 M.
Answer 13:
Assume the rate law has the form:
rate = k[F2]x[ClO2]y

To determine the order of the reaction with respect to F2, find two experiments in which the [ClO2] is
held constant. Compare the data from experiments 1 and 3. When the concentration of F 2 is doubled, the
reaction rate doubles. Thus, the reaction is first-order in F2.

To determine the order with respect to ClO2, compare experiments 1 and 2. When the ClO 2
concentration is quadrupled, the reaction rate quadruples. Thus, the reaction is first-order in ClO2.

The rate law is:


rate = k[F2][ClO2]

The value of k can be found using the data from any of the experiments. If we take the numbers from the
second experiment we have:

rate 4.8  10−3 M/s


k = = = 1.2 M −1s−1
[F2 ][ClO2 ] (0.10 M )(0.040 M )
Answer 13:

Verify that the same value of k can be obtained from the other sets of data.

Since we now know the rate law and the value of the rate constant, we can calculate the rate at any
concentration of reactants.

rate = k[F2][ClO2] = (1.2 M−1s−1)(0.010 M)(0.020 M) = 2.4  10−4 M/s


Question 14:
➢ Consider the reaction
X+Y→Z

From the following data, obtained at 360 K, (a) determine the order of the
reaction, and (b) determine the initial rate of disappearance of X when the
concentration of X is 0.30 M and that of Y is 0.40 M.

Initial Rate of Disappearance of X (M/s) [X] (M) [Y] (M)


0.053 0.10 0.50
0.127 0.20 0.30
1.02 0.40 0.60
0.254 0.20 0.60
0.509 0.40 0.30
Answer 14:
Strategy: We are given a set of concentrations and rate data and asked to determine the order of the
reaction and the initial rate for specific concentrations of X and Y. To determine the order of the
reaction, we need to find the rate law for the reaction. We assume that the rate law takes the form
rate = k[X]x[Y]y

How do we use the data to determine x and y? Once the orders of the reactants are known, we can
calculate k for any set of rate and concentrations. Finally, the rate law enables us to calculate the rate at
any concentrations of X and Y.

Solution:
(a) Experiments 2 and 5 show that when we double the concentration of X at constant concentration of
Y, the rate quadruples. Taking the ratio of the rates from these two experiments

rate5 0.509 M/s k (0.40) x (0.30) y


=  4 =
rate2 0.127 M/s k (0.20) x (0.30) y

Therefore,
(0.40) x
= 2x = 4
x
(0.20)

or, x = 2. That is, the reaction is second order in X. Experiments 2 and 4 indicate that doubling [Y]
at constant [X] doubles the rate. Here we write the ratio as

rate4 0.254 M/s k (0.20) x (0.60) y


= = 2 =
rate2 0.127 M/s k (0.20) x (0.30) y
Therefore,
(0.60) y
= 2y = 2
y
(0.30)

or, y = 1. That is, the reaction is first order in Y. Hence, the rate law is given by:
rate = k[X]2[Y]

The order of the reaction is (2 + 1) = 3. The reaction is 3rd-order.


Answer 14:

(b) The rate constant k can be calculated using the data from any one of the experiments. Rearranging
the rate law and using the first set of data, we find:
rate 0.053 M/s
k = = = 10.6 M −2s −1
2 2
[X] [Y] (0.10 M ) (0.50 M )

Next, using the known rate constant and substituting the concentrations of X and Y into the rate
law, we can calculate the initial rate of disappearance of X.
rate = (10.6 M−2s−1)(0.30 M)2(0.40 M) = 0.38 M/s
Question 15:
➢ Consider the reaction
A→B

The rate of the reaction is 1.6 × 10−2 M/s when the concentration of A is
0.35 M. Calculate the rate constant if the reaction is
(a) first order in A, and
(b) second order in A.
Answer 15:
(a) For a reaction first-order in A,

Rate = k[A]

1.6  10−2 M/s = k(0.35 M)

k = 0.046 s−1

(b) For a reaction second-order in A,

Rate = k[A]2

1.6  10−2 M/s = k(0.35 M)2


k = 0.13 /Ms
Question 16:
➢ The thermal decomposition of phosphine (PH3) into phosphorus and
molecular hydrogen is a first-order reaction:

4PH3(g)→P4(g)+6H2(g)

The half-life of the reaction is 35.0 s at 680°C. Calculate


(a) the first-order rate constant for the reaction and
(b) the time required for 95 percent of the phosphine to decompose.
Answer 16:
(a) Strategy: To calculate the rate constant, k, from the half-life of a first-
order reaction, we use Equation (13.6) of the text.
Solution: For a first-order reaction, we only need the half-life to calculate the
rate constant. From Equation (13.6)

0.693
k =
t1
2
Answer 16:
(b) Strategy: The relationship between the concentration of a reactant at different
times in a first-order reaction is given by Equations (13.3) and (13.4) of the text. We
are asked to determine the time required for 95% of the phosphine to decompose. If
we initially have 100% of the compound and 95% has reacted, then what is left must
be (100% − 95%), or 5%. Thus, the ratio of the percentages will be equal to the ratio
of the actual concentrations; that is, [A]t/[A]0 = 5%/100%, or 0.05/1.00.
Solution: The time required for 95% of the phosphine to decompose can be found
using Equation (13.3) of the text.

[A]t
ln = − kt
[A]0

(0.05)
ln = − (0.0198 s−1 )t
(1.00)

ln(0.0500)
t = − = 151 s
−1
0.0198 s
Question 17:
➢The rate constant for the second-order reaction

2NO2(g)→2NO(g)+O2(g)
is 0.54/M.s at 300°C. How long (in seconds) would it take for the
concentration of NO2 to decrease from 0.62 M to 0.28 M?
Answer 17:

1 1
= + kt
[A] [A]0

1 1
= + 0.54t
0.28 0.62
t = 3.6 s
Question 18:
➢The rate constant of a first-order reaction is 4.60 x 1024 s-1 at 350 ºC. If the
activation energy is 104 kJ/mol, calculate the temperature at which its rate
constant is 8.80 x 1024 s-1.
Answer 18:
Use a modified form of the Arrhenius equation to calculate the temperature at
which the rate constant is 8.80  10−4 s−1. We carry an extra significant figure
throughout this calculation to minimize rounding errors.
k E  1 1
ln 1 = a  − 
k2 R  T2 T1 

 4.60  10−4 s−1  1.04  105 J/mol  1 1 


ln   =  − 
 8.80  10−4 s−1  8.314 J/mol  K  T2 623 K 
 

 1 1 
ln(0.5227) = (1.251  104 K)  − 
 T2 623 K 

1.251  104 K
−0.6487 + 20.08 =
T2

19.43T2 = 1.251  104 K

T2 = 644 K = 371C
Question 19:
➢ Consider the first-order reaction

CH3NC(g)→CH3CN(g)

Given that the frequency factor and activation energy for the reaction are
3.98 × 1013 s−1 and 161 kJ/mol, respectively, calculate the rate constant
at 600°C.
Answer 19:
We use the Arrhenius equation to calculate the rate constant at a temperature
of 600ºC.

 161000 J/mol 
− 
(8.314 J/molK)(873 K) 
k = Ae− Ea /RT = (3.98  1013 s−1 ) e  = (3.98  1013 s−1 )(2.325  10−10 )

k = 9.25  103 s−1