192 Acid-Base Chemistry

Thus
Silica in the form of H3Si04- = a,CT,si = 0.58 x 1.33 x 10"
= 0.77 X 10" eq/liter
Alkalinity due to silicate = 0.77 x 10" eq/liter
'0.77 X 10"^
-i '
X 100= 19.2 percent
4 X 10"
A l kal i ni ty due to hydroxi de =0.44 x 10" eq/ liter
0.44 X 10"\
^^jQ-4 I X 100= 11.0percent
A l kal i ni ty due to carbonate and bi carbonate =100-(19.2 -1-11.0)
= 69.8 percent
Therefore, i n thi s water a si gni fi cant fracti on of the total al kal i ni ty (almost 20
percent) is due to the si l i cate system.
Many i nteresti ng aspects of the carbonate system occur i n connecti on
wi th heterogeneous systems contai ni ng carbonate sol i ds and sol ubl e
:arbonate compl exes. These topi cs are deal t wi th i n the next two chapters.
1.14. PROBLEMS
1. Cal cul ate the pH of the fol l owi ng perchl ori c aci d, HCI O4, solutions-
-'' (a) 10-^M.
(b) 10- M.
t
2. Cal cul ate the pH of the fol l owi ng potassi um hydroxi de, KOH, sol uti ons:
. (a) 10" M.
(b) 10-5 M.
3. A rsenious aci d is a weak aci d
HASO2 ^ H+- h A sO^-; K, = 10' "
If 10"^ moles of the herbi ci de NaAsOz, are added to 1 l i ter of di sti l l ed water
at 25C, what is the resul ti ng pH? Determine by sol vi ng the appropri ate set
of equati ons anal yti cal l y^
I . (a) A sol uti on of 10"= mole of sodi um propi onate (CHaCHpCOO Na) is added
to 1 l i ter of di sti l l ed water. If the pK, = 4.87 for propi oni c aci d, what i s
the sol uti on pH? Solve the appropri ate set of equati ons anal yti cal l y and
graphi cal l y and compare the resul ts,
(b) Propionic aci d i s a common consti tuent of anaerobic di gesters. If the pH
of the digester contents is 7.6, what percentage of the total amount of
propi oni c aci d is i oni zed at 25C?
A queous free chl ori ne i s hypochlorous aci d, HOCl , and hypochl ori te i on,
OCl ,-wi th the rel ati ve amounts dependi ng on the pH of the sol uti on.
Problems 193
(a) Gi ven that pK, = 7.5 for HOCl at 25C, what is the pH of a sol uti on
prepared by addi ng 10^^mole of NaOCl to 1 l i ter of water?
(b) What is the pH at whi ch 50 percent of the total free chl ori ne i s present as
HOCl?
(c) What is the pK^for OCl and to what reacti on does thi s constant appl y?
Neglect i oni c strength effects; temperature = 25C.
6. A sol uti on of 10"^ mole of Na2HP04i s added to 1 l i ter of sol uti on.
(a) Wri te the mass balances for Na and PO 4, Cr.Na. andCr.POi
(b) Wri te the proton condi ti on.
(c) Wri te the charge bal ance.
7. What pH results when 10" mole of NaH2P04are added to 1 l i ter of di sti l l ed
water? The temperature = 25C; assume that fi = 10"^ after the addi ti on.
Compare the val ue obtai ned when i oni c strength effects are taken i nto
account wi th that cal cul ated when i t i s negl ected. (See Fi g. 3-4 for acti vi ty
coefficients.)
8. What i s the pH of a sol uti on that i s prepared by addi ng 10^^mole of H ai CO,
to 1 l i ter of water? The temperature = 15C; /j. = 0. (See Tables 4-2 and 4-7
for equi l i bri um constants.) Compare thi s val ue wi th that obtai ned if the
temperature i s 25C.
9. What is the pH of a 10'^M K H SO 4 sol uti on at 25C; M = 0?
10. Usi ng ei ther the tabl e or the equati ons i n A ppendi x 1, cal cul ate
(a) ao and a, for hydrofl uori c aci d, HF, at pH 4.2.
(b) ao. i. and for H 2COI at pH 6.6. [Incl ude both approxi mate (0.05) and
exact val ues.]
(c) ao, a,, aj , and 03 for H3PO4 at pH 8.0. A ssume that acti vi ty effects are
negl i gi bl e and the temperature is 25C.
11. Cal cul ate the a val ues as requi red i n Problem 4-10 gi ven that the ionic
strength is 0.01.
12. 2.5 X 10-' mole of NHj.^,, and 2.5 x 10"' mole NaOH are added to 1 l i ter of
di sti l l ed water at 25C. What i s the pH if = 0?
13. I Q-^ moles NH4AC and 10^^moles NaOH are added to 1 l i ter of water at 25C.
What i s the pH if /x = 0?
14. What is the pH of a 25C sol uti on contai ni ng 10"^moles NaHCOj and 2 x 10"'
mole NH3 per l i ter if /x = 10"^?
15. A ni tri c aci d sol uti on, pH = 2.7, resul ts from NO, removal from a stack gas.
Neglect ionic strength effects and the temperature is 25C.
(a) How much NojCOa must be added to neutral i ze thi s sol uti on pri or to
discharge? (The fi nal pH i s 8.3. A ssume that no weak aci ds are present
i n the scrubber water.)
Hint: What i s the predomi nant carbonate species at pH 8.3?
(b) What i s the buffer i ntensi ty of the fi nal solution?
194 Acid-Base Chemistry
16. How much soda ash, NapCOa, in moles/ liter is required to neutralize a pickle
liquor solution containing 10" mole H2S04/ liter? Assume that the H2SO4 wi l l
react only with the NazCOa and that the pH after neutralization is 8.3.
17. An experiment is to be conducted on breakpoint chlorination (the oxidation
of ammonia by chlorine) i n which it is desired to maintain the pH constant
wi thi n 0.5 units of the i ni ti al pH of 8. Make the assumption that al l of the
ammonia is i n the NH4+ form (a reasonable assumption, since the pK, of
NH4+ is 9.3 and the pH of interest is pH 8). The breakpoint reaction between
C I 2 and NH3 proceeds as follows:
3C I 2 + 2NH4+ ^N2,9, + 8H+ + 6C1-
The maximum amount of ammonia that wi l l be used in the experiments is
12.5 mg as N/ liter (0.89 x 10"^ moles/ liter). Select an appropriate acid-
conjugate base pair and determine the concentration of it that wi l l control
the pH to wi thi n 0.5 units of 8.0 during the reaction. Neglect ionic strength
effects; the temperature = 25C. Determine the buffer intensity of this solution.
{Note: There is a detailed discussion of the breakpoint chlorination reaction
i n Chapter 7.)
1^ An industrial wastewater is to be discharged to a receiving stream with a
pH of 8.3 and a total al kal inity = 2 x 10"^ eq/ liter. The wastewater contains
5 X 10"^M H2SO4, and the pH of the stream should not be permitted to drop
below 6.3.
(p) What is the maximum dil ution ratio (volume waste/ volume stream water)
that can be used for discharge of the wastewater?
(b) What is the buffer intensity of the solution at pH 6.3?
19. A sample of natural water contains 1 x 10"^ M CO ^^ and 3 x 10"^ M HCOj-.
(a) As the pH is lowered during the al kal inity titration, at what pH is the C O2
i n solution i n equil ibrium wi th atmospheric C O2?
(b) What is the pH of the total al kal inity equivalence point, pHco^? (Neglect
dil ution effects.) Give your answer to nearest 0.1 pH unit.
(c) If 50 percent of the C O2 formed during the titration "escapes," what is the
"new" pH of the total al kal inity equivalence point?
^ A sample of\ natural water that has been equilibrated wi th CaCOais, is
isolated from its surroundings. I ndicate whether the addition of small
quantities of the fol l owing wi l l increase, decrease, or have no effect on the
total al kal inity or total acidity and state very briefly why. Neglect ionic
strength effects.
(a) HCl . ^ ('b) FeCla.
(c) Na2S04. (d) C O2. '
(e) Na2C03. ^^ >
21. A natural water has the fol l owing partiai analysis:
pH = 8.3 [C a2+] = 5 x 10" M
[HC O3-] = 3 X 10-3 ^ []y[g2+j ^ J ^ 10-4
[C O2,,,,] = 3 X 10-= M [S04=-] = 1 X 10" M
Additional Readings 1
(a) What volume of O.O2NH2SO4 is required to titrate a 100-ml sample to tl
total al kal inity endpoint? What is the total al kal inity in eq/ liter and
mg/ liter as CaCOj?
(b) A waste containing 10^ moles NaOH/ liter is to be discharged to th
water. The pH cannot be raised above 9.5. What is the maximum numb
of liters of waste that can be added to each liter of the natural wate
22. A partial water analysis is given as follows:
C O2 = 44 mg/ liter [CI "] = 1 x 10-^ M
[HC O3 ] = 2 x 10-3 M [SO4'-] = 1 x 10" M
(a) What is the solution pH and CO ^^' concentration?
(b) What is the caustic, carbonate, and total al kal inity (in eq/ liter and in m
liter as CaC03)?
(c) What is the mineral, C O2, and total acidity (in eq/ liter)?
(d) What is the pH if 5 x 10" mole OH" (as NaOH) are added per liter of t
above sample?
23^^^ifty ml of a natural water sample is titrated with 0.02 N H2SO4. The titro
volume required to titrate to pH 8.3 is 6 ml and an additional 8 ml is requir
to'titrate to pH 4.3.
(a) What is the caustic, carbonate, and total al kal inity in meq/ liter?
(b) What is the mineral, C O2, and total acidity i n meq/ liter?
.(c) What is CT.C03?
(d) What is pHco^ and pHcoj^ (to the nearest 0.1 pH unit)?
(e) What is [H+], [OH~], [C O3'- ], [HC O3-] and [HjCO^] in the original sampl
Calculate using both the approximate method described i n Section 4.i;
and the exact procedure and compare the results.
24. A solution has a carbonate al kal inity of 1 meq/ liter and a total al kal inity
6 meq/ liter. The ionic strength of the solution is 10^^ M and the temperati
is 40C. Calculate [H+], [HC O3- ], and [COj'] neglecting ionic strength effe(
and compare with the values obtained when corrections are made for ioi
strength effects. Use the constants given in Tables 4-2 and 4-7 for yc
calculations.
25^ I n some regions carbonate-bearing minerals are lacking i n the earth and t
^ lakes i n these regions have a low al kal inity. Acid rains, resulting fr<
conversion of industrial SO2 emissions to H2SO4, can cause significant
depressions in such lakes and may result in fish kil l s. What volume of a<
rain, pH = 4.0, is required to lower the pH of a lake to 6.7? The lake ha:
volume of 20 x 10^ft^, a pH = 7.0, and an al kal inity of 30 mg/ liter as CaCC
4.15. ADDI TI ONAL READI NG