CHEM

230 Sp18 PREP 4 blank p1

109) A weak acid HA (molar mass 67.1) is 7% ionized at equilibrium. The aqueous solution has a density
of 1.02 g/mL.

a) What is the i factor?

i=
4

b) The freezing point of the solution was measured to be -2.587oC. What is the concentration of
the weak acid? (kF H2O = 1.86 (K kg)/mol)

mol/L 8

c) What is the Ka of the acid?

Ka =
8
d) What is the pH of the solution?

pH =
2

CHEM 230 Sp18 PREP 4 blank p2

129) Consider an aqueous solution of NH4HSO4. Kb NH3 = 1.8x10-5; Ka2 H2SO4 = 1.2x10-2

a) Writing out two equilibria (one for each ion interacting with water) with its corresponding K value.

b) Combine your answers from part a) into one overall equilibrium. Find its K value.

c) Using your answer from part b) find the pH of a 0.17 M aqeuous solution of NH4HSO4.

10
pH =

CHEM 230 Sp18 PREP 4 blank p3

171) Consider ideal 0.10 m aqueous solutions of the five solutes listed below. Assume the salts are
completely soluble.
BaI2 BaS CoCl3 H2Te Na2Se

a) Rank the solutions in order of increasing vapor pressure. Write the formula for one solute in 10
each box.
< < < <
lowest vapor highest vapor
pressure pressure

b) Consider the acidity or basicity of the solutions described above, write the formula of each of the
five solutes into the appropriate box in the table below.

acidic basic neutral cannot determine

10

c) Which of the following solutions has the smallest change in entropy due to the salt dissolving?
Again assume complete dissolution but consider real solutions. (Circle one)
0.3 m KClO4 (aq) 0.2 m BaI2(aq) they experience the same change in entropy
4

d) On the plot to the right:

1) Sketch the Gibbs free energy vs. temperature for
an aqueous solution of KClO4 (ΔHsol = 51 kJ/mol).
2) Show the y-intercept relative to pure water. G
3) Indicate and label the freezing point of the solution.

Tf pure
T 6


456) On the Gibbs Free Energy vs. Temperature graph,
Gibbs Free Energy

add a line for each of the following ideal solutions:

A) 0.1 M HCl(aq)
bp pure water
B) 0.1 M NaOCl(aq)
C) 0.1 M H2S(aq)

Label the boiling point for each solution with the letter
of the solution.
Temperature

CHEM 230 Sp18 PREP 4 blank p4

225) a) 2.55 g of weak acid HA (MW = 85.1 g/mol) dissolves in 250.0 g of water to form a solution with a
density of 1.04 g/mL and a freezing point of -0.257 oC. (kF H2O = 1.86 (K kg)/mol). What is the pH?

pH =
12

Water is added to the solution described in part a. (Circle one answer in each box)

b) The pH when water is added will be: higher lower same cannot determine

c) The freezing point when water is added will be: higher lower same cannot determine

d) The van't Hoff i when water is added will be: higher lower same cannot determine

e) The Ka of HA when water is added will be: higher lower same cannot determine

258) The pH of water at 25oC is 7. The pH of water at 37oC is 6.8. The autoionization of water is
(Circle one): endothermic exothermic cannot be determined with the information given
4

CHEM 230 Sp18 PREP 4 blank p5

245) Nitride (N-3) is a strong base. When nitride is added to water, the following reaction takes place:
N-3(aq) + 3 H2O(l) --> 3 OH -(aq) + NH3(aq)
a) What is the pH when 1.00 g of lithium nitride (Li3N, MW = 34.83) is added to 500. mL of water?
(Consider only the OH- produced by N-3.)

6
pH =

b) Under the same conditions as part a what is the equilibrium concentration of ammonium [NH4+] ?
(The pKa of NH4+ = 9.24)

12
[NH4+] = M

283) At 37oC, the dissociation constant Kw of water is 2.5 x10-14. What is the pH of a 1x10-5 M aqueous
NaOH solution at 37oC?

10
pH =

CHEM 230 Sp18 PREP 4 blank p6

276) Refer to the data in the box to the right for all of the pKa
problems on this page. chlorous acid HClO2 2.00
a) Consider 0.05M aqueous solutions of each of the nitrous acid HNO2 3.37
+3
Cr as Cr(H2O)6 3.89
seven compounds listed here:
NaNH2 NaH Cr(NO3)3
pyridinium ion C5H5NH+ 5.24
NaClO2 C5H5N
carbonic acid H2CO3 6.37,10.25
Na2CO3 AgNO3
ammonium NH4+ 9.25
Rank the solutions in order of increasing pH: (Write the name of one solute in each box.) 6

< < < < < <

lowest pH highest pH

b) What is the equilibrium constant K for the following reaction?

C5H5N(aq) + HNO2(aq) <--> C5H5NH+(aq) + NO2-(aq)

6
K=

c) What is the pH of an aqueous solution that is 0.65M in NaNH2? What is the [NH4+(aq)] in that solution?

10
pH =

[NH4+] = M

CHEM 230 Sp18 PREP 4 blank p7

284) Evalute the solutes listed below. Consider the value of the solute's van't Hoff "i" factor in an ideal
aqueous solution. Write each solute in the box that corresponds to its "i" value.

i) SrCl2 ii) CH3NH3NO3 iii) H2S iv) NaH v) NaNH2

i<2 i=2 2<i<3 i=3 3<i<4 i=4 4<i

10


297) The salt NH4OH is considered to be a weak base. Rank the solute particles in an aqueous solution
of NH4OH in order of increasing concentration. Write one solute in each box.

< < <

lowest solute highest solute
concentration concentration

8


314) The Lewis structures and pKas for three acids are shown in the box.

a) Propose a brief explanation for why the pKa of HCN is so much H C N pKa = 9.4
greater than the pKas of HOCN and HSCN. H O C N pKa = 3.5

H S C N pKa = 1.1

b) Propose a brief explanation for why the pKa of HOCN is higher than the pKa of HSCN.

CHEM 230 Sp18 PREP 4 blank p8

Q 385
30
The first natural source of the mineral Na2H2SiO4 8H2O was discovered in Russia in 2007. It
happens to contain the anion that is the second conjugate base of orthosilicic acid (H4SiO4) a weak
diprotic acid (pKa1 = 9.5, pKa2 = 12.6). A 0.10 M aqueous solution of Na2H2SiO4 was prepared.
What are the van't Hoff "i" value of the salt Na2H2SiO4, the pH of the solution, and the concentration
of orthosilicic acid in the sample?

[H4SiO4] = M

van't Hoff "i" =

pH =

CHEM 230 Sp18 PREP 4 blank p9

Q 386

Consider 0.75 M aqueous, ideal solutions of each of the following solutes. Assmue all solutes are
completely soluble.
a) Rank the solutions in order of increasing pH. Write one solute in each box. (Hint: You will need to
recall the correlation between acid strength and structure to distinguish between two of the solutes.)

Al(ClO4)3, CuI, HCl, H2SO4, NaClO, NaClO2, NaNH2

< < < < < < 14

lowest pH highest pH

b) Assume that each of the following solutes acts ideally in water and dissolves completely. Write the
name of each solute in the box below corresponding to the correct van't Hoff "i" value or "i" range.

Al(ClO4)3, CuI, HCl, H2SO4, NaClO, NaClO2, NaNH2, Na2O, NaOH

i=1 1<i<2 i=2 2<i<3 i=3 3<i<4 i=4 4<i

16




222) Rank the following solutions in order of increasing boiling point. They are all ideal aqueous
solutions
that are 1.0 m in solute. Assume all salts are completely soluble at this molality.
Write the name of one solute in each box. Solutes:
C6H5NH2 H2SO4
AgClO4
Ca(HSO ) Cl2 K2O
4 2

< < < < <

lowest bp highest bp
12

CHEM 230 Sp18 PREP 4 blank p10

Q 407

Malic acid (C4H6O5, MW = 134.1) is a diprotic acid which was orignally isolated from apples;
thus part of its name comes from the Latin word for (evil) apple, malum. O
HO
a) At 25oC, 59.20 g of solid malic acid will dissolve in 100 g of water to OH
O H OH
form a saturated solution with a density of 1.250 g/mL. What is the pH
of this solution? malic acid
b) What is the concentration of malate (C4H4O5-2) in this solution? pKa1 = 3.40
pKa2 = 5.11
MW = 134.10

pH =
[C4H4O5-2] M
20

CHEM 230 Sp18 PREP 4 blank p11

Q 408

15
Refer to the data about diprotic malic acid in the table to answer questions a-d.
(Circle one answer in each box.) 20oC 25oC
pKa1 3.40 3.51
a) The ΔH for the dissociation of the first proton for malic acid is:
pKa2 5.03 5.11
ΔH < 0 ΔH = 0 ΔH > 0 cannot be determined
solubility (g/L) 558 592
in water

b) A solution of malic acid is prepared by dissolving 500 g of malic acid in 1.0 L of water. The
solution is heated from 20oC to 25oC. As the solution is heated, the van't Hoff "i" factor:
increases decreases stays the same cannot be determined

c) A saturated solution of malic acid is prepared. When more solid malic acid is added to the
solution, the pH of the solution:
increases decreases stays the same cannot be determined

d) The pH of a saturated solution of malic acid at 20oC would be

lower higher the same as cannot determine without calculations
than the pH of a saturated solution of malic acid at 25oC.

As part of the process of making red wine, malolactic fermentation takes place, converting malic acid
to lactic acid (C3H6O3), a monoprotic acid with a pKa@ 25oC of 3.85.
e) Assuming that all malic acid in a solution is converted to lactic acid (taking place under a
constant temperature of 25oC.) The pH of the lactic acid solution will be

lower higher the same as cannot determine than the pH of the malic acid solution.

Q 409

Assume that all salts included in the problem are completely soluble and that all solutions (A-G) are
aqueous and act idealy.

A) 1.0 m Ca(OH)2 a) List the letters of ALL solutions that have the same freezing point
B) 0.75 m Na3PO4 as a 1.0 m CaCl2(aq) solution:

C) 1.0 m CaF2 b) Which of the solutes (A-G) has the largest van't Hoff "i"?
D) 1.0 m H2SO4 Write the letter here:
E) 1.0 m K2O
c) List the letters of ALL solutions B-G that have the same pH as
F) 2.0 m KOH
solution A:
G) 1.5 m HClO4
d) Write the letter of the solution with the lowest pH:

e) Write the letters of ALL solutions that have solutes that are weak
bases:
15

CHEM 230 Sp18 PREP 4 blank p12

Q 457) Consider the ideal aqueous solutions that are each 0.1 M in solute listed below:
(Write the letter/s of the correct solution/s in each box.)
A) Na3AsO3
B) NaHSO4 a) The solution with the highest freezing point:
C) TiNO3
D) Na2C2O4 b) The solution with the highest pH:
E) Li2O
F) H2CO3 c) List the solution/s that have pH = 7:
G) Al(ClO4)3
d) List the solution/s with a pH < 7:

e) List the solutions with a van't Hoff i factor that is an integer:

16

Use the data in the box to help answer the following questions. pKa
CH3SO3H - 2.6
Q 486 HNO3 - 1.3
H2SO3 1.9, 7.21
HNO2 3.29
NH4+ 9.24

2) a) Rank 0.01 M solutions of the following solutes in order of increasing pH. Assume all solutes are
completely soluble and all salts dissociate completely. Write one solute in each box.

CH3SO3H, H2SO3, NaNO2, Na2SO3, NaSO3CH3, NH3

< < < < <

lowest pH highest pH
10

b) Rank 0.01 m solutions of the following solutes in order of increasing boiling point. Assume all solutes
are completely soluble and all salts dissociate completely. Write one solute in each box.

Ag2SO4, Ca(OH)2, H2SO3, LiIO3, NH3 NiNO3

< < < < <

lowest bp highest bp
10

CHEM 230 Sp18 PREP 4 blank p13

Q 487) A 0.5217 M aqueous solution of Na2CrO4 has a pH = 10.1 and [H2CrO4] = 1.05x10-15.
a) Find pKa1 and pKa2 for H2CrO4. (Hint: Start with the CrO4-2 equilibrium in water. You may assume
that the shortcut will work for second equilibrium.)

16
H2CrO4 pKa1 =

H2CrO4 pKa2 =

In spite of being a group 1 salt, Na2CrO4 has limited solubility. Its solubility increases with increasing
temperature. A saturated aqueous solution of Na2CrO4 is at 25oC. Circle one answer in each box.

b) Water is added at 25oC and solid remains at the new equilibrium. 3

The pH is higher lower the same at the new equilibrium than/as it was at the original equilibrium.

c) The solution is heated and solid remains at the new equilibrium. 3

The pH is higher lower the same at the new equilibrium than/as it was at the original equilibrium.

CHEM 230 Sp18 PREP 4 blank p14

2 a) Rank the 0.1 M aqueous solutions with solutes A-E in pKa1 pKa2
order of increasing pH. Assume that all salts are completly H2SO4 1.92
soluble and all solutions act ideally. Write one solute in each box. H2SO3 1.81 6.91
A) H2SO4 H3PO4 2.12 7.21
B) NaHSO4
C) H2SO3
< < < <
D) NaHSO3
E) H3PO4 lowest pH highest pH
10
Write <, >, =, or X (for cannot be determined) in each box below.

b) van’t Hoff i factor for H2SO3 van’t Hoff i factor for NaHSO3

c) van’t Hoff i factor for NaHSO4 van’t Hoff i factor for NaHSO3

d) [SO4-2] in 0.1 M aqueous H2SO4 [SO4-2] in 0.1 M aqueous NaHSO4

e) pKa H2PO4- pKb H2PO4-

f) pKa HPO4-2 pKb HPO4-2

g) [H+] in an aqueous solution of PO4-3 [OH-] in an aqueous solution of PO4-3 12

3) Ca(OH)2 has a pKsp = 11.15. What is the pH of a saturated aqueous solution of Ca(OH)2? 10

pH =

CHEM 230 Sp18 PREP 4 blank p15

1) a) Hydrogen peroxide O O has a larger Ka than water. Briefly explain this trend in acidity.
H H

6
20

CHEM 230 Sp18 PREP 4 blank p16

Q 488
7.0 mL of an aqueous solution of H2SO3 is titrated with indicator acidic pKin basic
0.10 M NaOH(aq). A sketch of the titration curve is shown. color color
bromocresol green yellow 4.6 blue
azolitmin red 6.4 blue
pH D 20.0 mL, pH = 10.1 thymol phthalein colorless 9.9 blue
C
alizarine yellow yellow 11.1 red
A B 15.0 mL, pH = 7.19 Fiil in the blank.
10.0 mL, pH = 4.49
a) pKa1 H2SO3 = ____________
5.0 mL, pH = 1.78 2
mL NaOH added b) pKa2 H2SO3 = ____________ 2

c) Briefly explain why a mixture of bromocresol green and thymol phthalein would not be an effective
indicator to identify the two stoichiometric points of the titration.

2
4
d) A mixture of indicators must be used in order to identify both stoichiometric points during the titration.
Write in the two indicators that will effectively accomplish this:

e) What was the initial concentration of the H2SO3 solutions that was titrated? 4

[H2SO3] = M
14
f) What is the pH when 10.0 mL of 0.5 M H2SO3(aq) is mixed with 1.14 mL of 4.0 M NaOH(aq)?
Go ahead and use the shortcut...it will work. :)

pH =

CHEM 230 Sp18 PREP 4 blank p17

Q460

Consider the two titrations described below. Write < , >, = , or X (for cannot be determined) in each box
below comparing the two titrations.

A) 10.0 mL of 0.20 M aqueous acetic acid (pKa = 4.75) titrated with 0.10 M NaOH(aq)
B) 20.0 mL of 0.10 M aqueous lactic acid (pKa = 3.08) titrated with 0.10 M NaOH(aq)

a) initial pH acetic acid solution initial pH lactic acid solution

b) pH at the 1/2 stoichiometric point pH at the 1/2 stoichiometric point

of the acetic acid of the lactic acid

c) volume of NaOH needed to reach the volume of NaOH needed to reach the
stoichiometric point of the acetic acid stoichiometric point of the lactic acid

d) pH at the stoichiometric pH at the stoichiometric

point of the acetic acid point of the lactic acid

e) moles of OH-(aq) when 23.0 mL of moles of OH-(aq) when 23.0 mL of

NaOH are added to the acetic acid NaOH are added to the lactic acid

f) the exact pH when 25.0 mL of NaOH the exact pH when 25.0 mL of NaOH
has been added to the acetic acid has been added to the lactic acid 12

g) Find th pH of the acetic acid solution when it has reached the stoichiometric point of the titration.

10
pH =

CHEM 230 Sp18 PREP 4 blank p18

Q411

a) On the graph below use a solid line to sketch a titration curve for 10.0 mL of a 0.1 M solution of
malic acid (pKa1 = 3.51 and pKa2 = 5.11) titrated with 0.1 M NaOH(aq).

b) On the same figure, use a dashed line to sketch the titration curve for 10.0 mL of a 0.1 M aqueous
solution of lactic acid (pKa = 3.85) titrated with 0.1 M NaOH(aq).

c) You can approximate initial pH.

d) Be sure that all 1/2 SP and SP are at accurate volumes.
e) On the graph be sure to label the pH at any 1/2 SP.
10
.
f) Calculate the pH of the malic
acid solution when 30 mL of the

:
0.1M NaOH(aq) have been added.

: -

PH 7 -

5 -

÷ -

's io K do ab so .

ML NAOH added

pH @ 30 mL NaOH added:

CHEM 230 Sp18 PREP 4 blank p19

Q 355

H2CO3 pKa1 = 6.37; pKa2 = 10.25

20.0 mL of an aqueous solution of Na2CO3 is titrated with 0.25 M HCl(aq). All 20.0 mL of the HCl solution
that is available are used in the titration, but the titration has not reached its final end point. The titration
is continued with 0.05 M HNO3(aq). It takes 20.0 mL of the HNO3 to reach the final end point.

a) What was the original concentration of the Na2CO3 solution?

6
[Na2CO3] = M

b) What is the pH of the titration solution when the final stoichiometric point is reached?

10
pH =

c) If the HCl solution had not run out (it the pH of the titration solution at the
greater than
was used for the entire titration) the pH final stoichiometric point when
less than
of the titration solution at the final HNO3 was used as described
stoichiometric point would be (Circle one) equal to above
4
d) The titration solution will have a pH = 7.0 during (Circle one):
i) The addition of the first 10.0 mL of HCl
ii) The addition of the second 10.0 mL of HCl
iii) The addition of the first 10.0 mL of HNO3
iv) The addition of the second 10.0 mL of HNO3
4

CHEM 230 Sp18 PREP 4 blank p20

303) (20 pts) Consider the three scenarios that follow:

Solution A [10.0 mL of 0.25 M formic acid (HCOOH, pKa = 3.75)] is titrated with 0.1 M NaOH
Solution B [10.0 mL of 0.25 M NaOH] is titrated with 0.1 M HCl

Solution C [25.0 mL of 0.1 M ammonia (NH3, pKb = 4.75)] is titrated with 0.1 M HCl

a) Rank the initial pH of the solutions b) Rank the pH at the stoichiometric point.
(before any titrant is added). (Place one letter A, B, or C in each box.)
(Place one letter A, B, or C in each box).
lowest
pH < < highest
pH
lowest
pH
< < highest
pH
3 3

c) Which solution, A or B, will require the greater d) Which solution, B or C will require the greater
volume of titrant added to reach the volume of titrant added to reach the
stoichiometric point? (Circle one) stoichiometric point? (Circle one)
A B both require the same B C both require the same
3 3

e) What is the pH at the stoichiometric point for titration of Solution A?

pH =
8

CHEM 230 Sp18 PREP 4 blank p21

299) Thymol blue (H2Tb) is an indicator that pKin1 = 1.7 pKin2 = 8.9
has two pKins. acid form = red acid form = yellow
basic form = yellow basic form = blue

An aqueous solution of H2Tb is titrated with

KOH, generating data to construct the
distribution diagram shown. For parts a-d, fill
in the information about the diagram.

a) pH = ________

b) Color of the thymol blue solution at this pH: ________

c) Color of the thymol blue solution at this pH: ________

d) Color of the thymol blue solution at this pH: ________

8

e) What is the pH of an aqueous solution that is 0.1 M Na2Tb?

12
pH =

f) What is the concentration of H2Tb in the 0.1 M aqueous solution of Na2Tb?

6
[H2Tb] = M

CHEM 230 Sp18 PREP 4 blank p22

268) a)Compare the two solutions by placing < , > , = , or X (for cannot be determined) in each box below.

0.5 M aqueous solution of H2CO3 0.5 M aqueous solution of H2SO3

(pKa1 = 3.6, pKa2 = 10.3) (pKa1 = 1.9, pKa2 = 7.21).

the pH of the 0.5 M H2CO3(aq) the pH of the 0.5 M H2SO3(aq) 3 each

the i factor of the 0.5 M H2CO3(aq) the i factor of the 0.5 M H2SO3(aq)

pH at the first 1/2 stoichiometric pH at the first 1/2 stoichiometric

point in the titration of 100 mL of point in the titration of 100 mL of
the 0.5 M H2CO3 with 0.5 M NaOH the 0.5 M H2SO3 with 0.5 M NaOH

mL of 0.5 M 0.NaOH added to reach mL of 0.5 M NaOH added to reach

the first stoichiometric point in the the first stoichiometric point in the
titration of 100 mL of the 0.5 M H2CO3 titration of 100 mL of the 0.5 M H2SO3

mL of 0.5 M NaOH added to 100 mL mL of 0.5 M NaOH added to 100 mL

of 0.5 M H2CO3 to reach a pH = 10 of 0.5 M H2SO3 to reach a pH = 10 15

b) A distribution diagram for H2SO3 is shown below. Identify the major specie/s in solution at each
point identified. major specie/s
mole fraction

major specie/s pH =

0 2 4 6 8 10
pH

CHEM 230 Sp18 PREP 4 blank p23

216) There has been a mix up in the titration lab. An aqueous solution of some substance was titrated
with either 1.0 M HCl or 1.0 M NaOH. The titration curve is shown below. What could the
substance have been?
(Circle the ONE best answer.) (CH ) NH H PO H S NaClO Na PO
3 2 3 4 2 2 3 4
4

pH

!
mL titrant added

b) List the most substantial ion/s in the solution being titrated at this point?

c) For the substance identified in part a, its pKa3 is approximately:

4

d) Circle a suitable indicator for the second stoichiometric point in this titration from the list below.
indicator pKin
thymol blue 1.7
bromocresol green 4.7
phenolphthalein 9.4
alizarin red 11.7 4

e) In order to determine the identity of the unknown substance, you search the database of titration
curves. When comparing the titration curve above with the ones in the database, which one of the
following criteria must match up identically in order to make an identification? (Circle the correct
answer.)

i) The initial pH
ii) The pH at the stoichiometric points
iii) The mL of titrant added at the stoichiometric points
iv) The pH at the 1/2 stoichiometric points
v) The mL of titrant added to reach the 1/2 stoichiometric points.
4

CHEM 230 Sp18 PREP 4 blank p24

20
Hydrogen peroxide (a weak acid) is sold in drug stores in a brown bottle containing 16 oz (473 mL)
of an aqueous solution (density 1.0 g/mL) of hydrogen peroxide. The entire contents of the bottle
are titrated with 0.5 M NaOH(aq) and it takes 834 mL of titrant to reach the stoichiometric point where
the solution has a pH = 12.62. b) What is the original concentration of H2O2(aq) in the bottle?
c) What is the pH at the 1/2-stoichiometric point?

[H2O2] = M

pH @ 1/2 SP