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21.2
Salts in Solution
Salt Hydrolysis
• A salt is an ionic compound that:
–comes from the anion of an acid
–comes from the cation of a base
–is formed from a neutralization reaction
–some neutral; others acidic or basic
• “Salt hydrolysis” - a salt that reacts with
water to produce acid or base
Salt Hydrolysis
• Hydrolyzing salts usually come from:
1. strong acid + weak base, or
2. weak acid + strong base
• Strong refers to the degree of ionization
• How do you know if it’s strong?
– Refer to the handout provided
(downloadable from my web site)
Salt Hydrolysis
• To see if the resulting salt is acidic
or basic, check the “parent” acid
and base that formed it. Practice
on these:
HCl + NaOH
H2SO4 + NH4OH
CH3COOH + KOH
Strong Acid + Strong base neutral solution
Strong acid + weak base acidic solution
(salt hydrolyzes acidic)
Weak acid + Strong base basic solution
(salt hydrolyzes basic)
Salt Hydrolysis
Buffers
• Buffers are solutions in which the
pH remains relatively constant,
even when small amounts of acid
or base are added
–made from a pair of chemicals: a
weak acid and one of it’s salts;
or a weak base and one of it’s
salts
Buffers
• ml HCl pH
• added unbuffered buffered
• 0 7.00 7.00
• 10 1.04 6.91
• 20 0.78 6.82
• 30 0.64 6.73
• 40 0.54 6.63
• 50 0.48 6.52
• 60 0.43 6.40
• 70 0.39 6.25
• 80 0.35 6.05
• 90 0.32 5.72
Buffers
ml HCl added
pH
buffered
unbuffered
Buffers
• A buffer system is better able to resist
changes in pH than pure water
• Since it is a pair of chemicals:
–one chemical neutralizes any acid
added, while the other chemical would
neutralize any additional base
–AND, they produce each other in the
process!!!
Buffers
• Example: Ethanoic (acetic)
acid and sodium ethanoate
(also called sodium acetate)
• Examples on page 628 of
these
• The buffer capacity is the
amount of acid or base that
can be added before a
significant change in pH
Buffers
• The buffers that are crucial to
maintain the pH of human blood are:
1. carbonic acid (H2CO3) & hydrogen
carbonate (HCO3
1-
)
2. dihydrogen phosphate (H2PO4
1-
) &
monohydrogen phoshate (HPO4
2-
)
– Table 21.2, page 629 has some
important buffer systems
Buffers
• How does the carbonic acid-
hydrogen carbonate buffer system
work?
IF there is base added:
H2CO3 + OH-
-------H2O + HCO3
-
If there is acid added:
HCO3
-
+ H+
--------H2CO3 ( which is a weak acid)
Solubility Products, KSP
• KSP expressions are used for ionic
materials that are only slightly
soluble in water
Look at chart on pg 631
• Their only means of dissolving is
by dissociation.
• AgCl(s) Ag+
(aq) + Cl-
(aq)
• KSP = [ Ag+
] [ Cl-
]
Solubility Products, KSP
• At equilibrium, our system is a saturated
solution of silver and chloride ions.
• The only way to know that it is
saturated it to observe some AgCl at the
bottom of the solution.
• As such, [AgCl] is a constant and KSP
expressions are really Keq x constant conc
of the solid so do not include the solid form
in the equilibrium expression.
• Chart on pg.632 shows Ksp for common
slightly soluble salts
• What is the concentration of silver
ions and chloride ions in a saturated
silver chloride solution at 250
C?
(Ksp= 1.8 x 10-10
)
Ksp=[Ag+
][Cl-
];
[Ag+
]=[Cl-
]
1.8 x 10-10
=x2
1.3 x 10-5
=x which is the conc. of silver
and chloride ions
Solubility Products, Ksp Problem
• Calcium flouride has a Ksp of 3.9 x 10-11
at
250
C. What is the flouride ion conc. At
equilibrium?
• CaF2------Ca2+
+ 2F-
Ksp=[Ca2+
][F-
]2
Since there are twice as many F-
as Ca2+
,
Ksp=[x][2x]2
=2x3
3.9 x 10-11
=4x3
3.9 x 10-11
/4=x3
9.8 x 10-12
=x3
2.1 x 10-4
=x=F-
Solubility Products, KSP, Problem
Common ion effect.
• This is an example of Le Châtelier’s
principle.
Common ion effectCommon ion effect
• The shift in equilibrium caused by the
addition of an ion formed from the solute.
Common ionCommon ion
• An ion that is produced by more than
one solute in an equilibrium system.
• Adding the salt of a weak acid to a
solution of weak acid is an example of this.
Common Ion Effect: Example
• PbCrO4(s) Pb2+
(aq) +CrO4(aq)
2-
If you add lead nitrate to this solution you
increase the lead(II) ion and equil shifts
to the left, and some lead(II) chromate
will precipite out. The Ksp will stay the
same.
The lead ion is called the “common ion”,
the lowering of the solubility of lead(II)
chromate is called the common ion
effect.
• If the ions concentrations are
multiplied together, [ion][ion],
and is greater than the Ksp,
then a precipitate will form.
Common Ion Effect
• The Ksp of silver iodide is 8.3 x 10-17
.
What is the iodide ion conc. Of a 1.00L
saturated solution of AgI to which
0.020mol of AgNO3 is added?
Ksp=[Ag+
][I-
]=x
Because Ksp is so small, x is insignificant
compared to 0.20mol of Ag+ so
8.3 x 10-17
=[0.20][x]
8.3x10-17
/0.20=4.2 x 10-15
M
Common Ion Effect: PROBLEM
• Predict whether barium sulfate will precipitate
when 0.50L of 0.002M Ba(NO3)2 mixes with
0.50L of 0.008M Na2SO4 to form a 1.0L
solution. Ksp of BaSO4 is 1.1 x 10-10
Find [Ba2+
] and [SO4
2-
] if this is > than Ksp,then
precipitation will occur
[Ba2+
] = .50L x .002M=.001mol/1L
[SO4
2-
]= .50L x .008M=.004mol/1L
.001 x .004= 4 x 10-6
which is greater than the
Ksp, so yes, BaSO4 will precipitate
Common Ion Effect: PROBLEM

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  • 2. Salt Hydrolysis • A salt is an ionic compound that: –comes from the anion of an acid –comes from the cation of a base –is formed from a neutralization reaction –some neutral; others acidic or basic • “Salt hydrolysis” - a salt that reacts with water to produce acid or base
  • 3. Salt Hydrolysis • Hydrolyzing salts usually come from: 1. strong acid + weak base, or 2. weak acid + strong base • Strong refers to the degree of ionization • How do you know if it’s strong? – Refer to the handout provided (downloadable from my web site)
  • 4. Salt Hydrolysis • To see if the resulting salt is acidic or basic, check the “parent” acid and base that formed it. Practice on these: HCl + NaOH H2SO4 + NH4OH CH3COOH + KOH
  • 5. Strong Acid + Strong base neutral solution Strong acid + weak base acidic solution (salt hydrolyzes acidic) Weak acid + Strong base basic solution (salt hydrolyzes basic) Salt Hydrolysis
  • 6. Buffers • Buffers are solutions in which the pH remains relatively constant, even when small amounts of acid or base are added –made from a pair of chemicals: a weak acid and one of it’s salts; or a weak base and one of it’s salts
  • 7. Buffers • ml HCl pH • added unbuffered buffered • 0 7.00 7.00 • 10 1.04 6.91 • 20 0.78 6.82 • 30 0.64 6.73 • 40 0.54 6.63 • 50 0.48 6.52 • 60 0.43 6.40 • 70 0.39 6.25 • 80 0.35 6.05 • 90 0.32 5.72
  • 9. Buffers • A buffer system is better able to resist changes in pH than pure water • Since it is a pair of chemicals: –one chemical neutralizes any acid added, while the other chemical would neutralize any additional base –AND, they produce each other in the process!!!
  • 10. Buffers • Example: Ethanoic (acetic) acid and sodium ethanoate (also called sodium acetate) • Examples on page 628 of these • The buffer capacity is the amount of acid or base that can be added before a significant change in pH
  • 11. Buffers • The buffers that are crucial to maintain the pH of human blood are: 1. carbonic acid (H2CO3) & hydrogen carbonate (HCO3 1- ) 2. dihydrogen phosphate (H2PO4 1- ) & monohydrogen phoshate (HPO4 2- ) – Table 21.2, page 629 has some important buffer systems
  • 12. Buffers • How does the carbonic acid- hydrogen carbonate buffer system work? IF there is base added: H2CO3 + OH- -------H2O + HCO3 - If there is acid added: HCO3 - + H+ --------H2CO3 ( which is a weak acid)
  • 13.
  • 14. Solubility Products, KSP • KSP expressions are used for ionic materials that are only slightly soluble in water Look at chart on pg 631 • Their only means of dissolving is by dissociation. • AgCl(s) Ag+ (aq) + Cl- (aq) • KSP = [ Ag+ ] [ Cl- ]
  • 15. Solubility Products, KSP • At equilibrium, our system is a saturated solution of silver and chloride ions. • The only way to know that it is saturated it to observe some AgCl at the bottom of the solution. • As such, [AgCl] is a constant and KSP expressions are really Keq x constant conc of the solid so do not include the solid form in the equilibrium expression. • Chart on pg.632 shows Ksp for common slightly soluble salts
  • 16. • What is the concentration of silver ions and chloride ions in a saturated silver chloride solution at 250 C? (Ksp= 1.8 x 10-10 ) Ksp=[Ag+ ][Cl- ]; [Ag+ ]=[Cl- ] 1.8 x 10-10 =x2 1.3 x 10-5 =x which is the conc. of silver and chloride ions Solubility Products, Ksp Problem
  • 17. • Calcium flouride has a Ksp of 3.9 x 10-11 at 250 C. What is the flouride ion conc. At equilibrium? • CaF2------Ca2+ + 2F- Ksp=[Ca2+ ][F- ]2 Since there are twice as many F- as Ca2+ , Ksp=[x][2x]2 =2x3 3.9 x 10-11 =4x3 3.9 x 10-11 /4=x3 9.8 x 10-12 =x3 2.1 x 10-4 =x=F- Solubility Products, KSP, Problem
  • 18. Common ion effect. • This is an example of Le Châtelier’s principle. Common ion effectCommon ion effect • The shift in equilibrium caused by the addition of an ion formed from the solute. Common ionCommon ion • An ion that is produced by more than one solute in an equilibrium system. • Adding the salt of a weak acid to a solution of weak acid is an example of this.
  • 19. Common Ion Effect: Example • PbCrO4(s) Pb2+ (aq) +CrO4(aq) 2- If you add lead nitrate to this solution you increase the lead(II) ion and equil shifts to the left, and some lead(II) chromate will precipite out. The Ksp will stay the same. The lead ion is called the “common ion”, the lowering of the solubility of lead(II) chromate is called the common ion effect.
  • 20. • If the ions concentrations are multiplied together, [ion][ion], and is greater than the Ksp, then a precipitate will form. Common Ion Effect
  • 21. • The Ksp of silver iodide is 8.3 x 10-17 . What is the iodide ion conc. Of a 1.00L saturated solution of AgI to which 0.020mol of AgNO3 is added? Ksp=[Ag+ ][I- ]=x Because Ksp is so small, x is insignificant compared to 0.20mol of Ag+ so 8.3 x 10-17 =[0.20][x] 8.3x10-17 /0.20=4.2 x 10-15 M Common Ion Effect: PROBLEM
  • 22. • Predict whether barium sulfate will precipitate when 0.50L of 0.002M Ba(NO3)2 mixes with 0.50L of 0.008M Na2SO4 to form a 1.0L solution. Ksp of BaSO4 is 1.1 x 10-10 Find [Ba2+ ] and [SO4 2- ] if this is > than Ksp,then precipitation will occur [Ba2+ ] = .50L x .002M=.001mol/1L [SO4 2- ]= .50L x .008M=.004mol/1L .001 x .004= 4 x 10-6 which is greater than the Ksp, so yes, BaSO4 will precipitate Common Ion Effect: PROBLEM