Acids and Bases

Stomach Acid & Heartburn

• the cells that line your stomach produce
hydrochloric acid
 to kill unwanted bacteria
 to help break down food
 to activate enzymes that break down food
• if the stomach acid backs up into your esophagus, it
irritates those tissues, resulting in heartburn
 acid reflux
 GERD = gastroesophageal reflux disease = chronic
leaking of stomach acid into the esophagus
 Properties of Acids
• sour taste
• react with “active” metals
 i.e., Al, Zn, Fe, but not Cu, Ag, or Au
2 Al + 6 HCl AlCl3 + 3 H2
 corrosive
• react with carbonates, producing CO2
 marble, baking soda, chalk, limestone
CaCO3 + 2 HCl CaCl2 + CO2 + H2O
• change color of vegetable dyes
 blue litmus turns red
• react with bases to form ionic salts
 Common Acids
Chemical Name Formula Uses Strength
Nitric Acid HNO3 explosive, fertilizer, dye, glue Strong
explosive, fertilizer, dye, glue,
Sulfuric Acid H2SO4 Strong
batteries
metal cleaning, food prep, ore
Hydrochloric Acid HCl Strong
refining, stomach acid
fertilizer, plastics & rubber,
Phosphoric Acid H3PO4 Moderate
food preservation
plastics & rubber, food
Acetic Acid HC2H3O2 Weak
preservation, Vinegar
Hydrofluoric Acid HF metal cleaning, glass etching Weak
Carbonic Acid H2CO3 soda water Weak
Boric Acid H3BO3 eye wash Weak
 Structures of Acids
• binary acids have acid hydrogens attached to
a nonmetal atom
HCl, HF
 Structure of Acids
• oxy acids have acid hydrogens attached to
an oxygen atom
H2SO4, HNO3
 Structure of Acids
• carboxylic acids have
COOH group
 HC2H3O2, H3C6H5O7
• only the first H in the
formula is acidic
 the H is on the COOH
 Properties of Bases
• also known as alkalis
• taste bitter
 alkaloids = plant product that is alkaline
 often poisonous
• solutions feel slippery
• change color of vegetable dyes
 different color than acid
 red litmus turns blue
• react with acids to form ionic salts
 neutralization
 Common Bases
Chemical Common
Formula Uses Strength
Name Name
sodium lye, soap, plastic,
NaOH Strong
hydroxide caustic soda petrol refining
potassium soap, cotton,
KOH caustic potash Strong
hydroxide electroplating
calcium
Ca(OH)2 slaked lime cement Strong
hydroxide
sodium
NaHCO3 baking soda cooking, antacid Weak
bicarbonate
magnesium milk of
Mg(OH)2 antacid Weak
hydroxide magnesia
detergent,
ammonium NH4OH, ammonia
fertilizer, Weak
hydroxide {NH3(aq)} water
explosives, fibers
 Structure of Bases
• most ionic bases contain OH- ions
NaOH, Ca(OH)2
• some contain CO32- ions
CaCO3 NaHCO3
• molecular bases contain structures
that react with H+
mostly amine groups
 Indicators
• chemicals which change color depending on the
acidity/basicity
• many vegetable dyes are indicators
 anthocyanins
• litmus
 from Spanish moss
 red in acid, blue in base
• phenolphthalein
 found in laxatives
 red in base, colorless in acid
 Ask Mulik
 Arrhenius Theory
• bases dissociate in water to produce OH- ions and
cations
ionic substances dissociate in water
NaOH(aq) → Na+(aq) + OH–(aq)
• acids ionize in water to produce H+ ions and anions
because molecular acids are not made of ions, they cannot
dissociate
they must be pulled apart, or ionized, by the water
HCl(aq) → H+(aq) + Cl–(aq)
in formula, ionizable H written in front
HC2H3O2(aq) → H+(aq) + C2H3O2–(aq)
 Arrhenius Theory

HCl ionizes in water, NaOH dissociates in water,

producing H+ and Cl– ions producing Na+ and OH– ions
 Hydronium Ion
• the H+ ions produced by the acid are so reactive they
cannot exist in water
 H+ ions are protons!!
• instead, they react with a water molecule(s) to produce
complex ions, mainly hydronium ion, H3O+
H+ + H2O  H3O+
 there are also minor amounts of H+ with multiple water
molecules, H(H2O)n+
 Arrhenius Acid-Base Reactions
• the H+ from the acid combines with the OH-
from the base to make a molecule of H2O
it is often helpful to think of H2O as H-OH
• the cation from the base combines with the
anion from the acid to make a salt
acid + base → salt + water
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
 Problems with Arrhenius Theory
• does not explain why molecular substances, like
NH3, dissolve in water to form basic solutions –
even though they do not contain OH– ions
• does not explain how some ionic compounds, like
Na2CO3 or Na2O, dissolve in water to form basic
solutions – even though they do not contain OH–
ions
• does not explain why molecular substances, like
CO2, dissolve in water to form acidic solutions –
even though they do not contain H+ ions
• does not explain acid-base reactions that take place
outside aqueous solution
 Brønsted-Lowry Theory
• in a Brønsted-Lowry Acid-Base reaction, an
H+ is transferred
 does not have to take place in aqueous solution
 broader definition than Arrhenius
• acid is H+ donor, base is H+ acceptor
 base structure must contain an atom with an
unshared pair of electrons
• in an acid-base reaction, the acid molecule
gives an H+ to the base molecule
H–A + :B  :A– + H–B+
 Brønsted-Lowry Acids
• Brønsted-Lowry acids are H+ donors
any material that has H can potentially be a
Brønsted-Lowry acid
because of the molecular structure, often one H in
the molecule is easier to transfer than others
• HCl(aq) is acidic because HCl transfers an H+ to
H2O, forming H3O+ ions
water acts as base, accepting H+

HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq)

acid base
 Brønsted-Lowry Bases
• Brønsted-Lowry bases are H+ acceptors
any material that has atoms with lone pairs can
potentially be a Brønsted-Lowry base
because of the molecular structure, often one atom
in the molecule is more willing to accept H+ transfer
than others
• NH3(aq) is basic because NH3 accepts an H+
from H2O, forming OH–(aq)
water acts as acid, donating H+
NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)
base acid
 Amphoteric Substances
• amphoteric substances can act as either an
acid or a base
have both transferable H and atom with lone pair
• water acts as base, accepting H+ from HCl
HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq)
• water acts as acid, donating H+ to NH3
NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)
 Brønsted-Lowry
Acid-Base Reactions
• one of the advantages of Brønsted-Lowry theory is that
it allows reactions to be reversible
H–A + :B  :A– + H–B+
• the original base has an extra H+ after the reaction – so
it will act as an acid in the reverse process
• and the original acid has a lone pair of electrons after
the reaction – so it will act as a base in the reverse
process
:A– + H–B+  H–A + :B
 Conjugate Pairs
• In a Brønsted-Lowry Acid-Base reaction, the
original base becomes an acid in the reverse
reaction, and the original acid becomes a base in
the reverse process
• each reactant and the product it becomes is
called a conjugate pair
• the original base becomes the conjugate acid;
and the original acid becomes the conjugate base
 Brønsted-Lowry
Acid-Base Reactions
H–A + :B  :A– + H–B+
acid base conjugate conjugate
base acid
HCHO2 + H2O  CHO2– + H3O+
acid base conjugate conjugate
base acid
H2O + NH3  HO– + NH4+
acid base conjugate conjugate
base acid
 Conjugate Pairs
In the reaction H2O + NH3  HO– + NH4+
H2O and HO– constitute an
Acid/Conjugate Base pair

NH3 and NH4+ constitute a

Base/Conjugate Acid pair
Ex 15.1a – Identify the Brønsted-Lowry Acids and
Bases and Their Conjugates in the Reaction

H2SO4 + H2O  HSO4– + H3O+

When the H2SO4 becomes HSO4, it lost an H+  so
H2SO4 must be the acid and HSO4 its conjugate base
When the H2O becomes H3O+, it accepted an H+  so
H2O must be the base and H3O+ its conjugate acid

H2SO4 + H2O  HSO4– + H3O+

acid base conjugate conjugate
base acid
Ex 15.1b – Identify the Brønsted-Lowry Acids and
Bases and Their Conjugates in the Reaction
HCO3– + H2O  H2CO3 + HO–
When the HCO3 becomes H2CO3, it accepted an H+ 
so HCO3 must be the base and H2CO3 its conjugate acid
When the H2O becomes OH, it donated an H+  so
H2O must be the acid and OH its conjugate base
HCO3– + H2O  H2CO3 + HO–
base acid conjugate conjugate
acid base
 • Identify the conjugate acid-base pairs in the
following:
H 2 PO 4 - (aq) + CO 3 -2 (aq) HCO 3 - (aq) + HPO4 2- (aq)

Base Conjugate Acid

Acid Conjugate base

H 2 PO 4 - has one more H + than HPO 4 2- and

CO 3 2- has one fewer H + than HCO 3 -

H 2 PO 4 - & HCO 3 - are acids

HPO 4 2- & CO 3 2- are bases

H 2 PO 4 - / HPO 4 2- is a conjugate acid - base pair

HCO 3 - / CO 3 2- is a conjugate acid - base pair
5/1/2019 27
 Practice – Write the formula for the
conjugate acid of the following
H2O

NH3

CO32−

H2PO41−
 Practice – Write the formula for the
conjugate acid of the following
H2O H3O+

NH3 NH4+

CO32− HCO3−

H2PO41− H3PO4
 Practice – Write the formula for the
conjugate base of the following
H2O

NH3

CO32−

H2PO41−
 Practice – Write the formula for the
conjugate base of the following
H2O HO−

NH3 NH2−

CO32− since CO32− does not have an H, it

cannot be an acid

H2PO41− HPO42−
 Arrow Conventions
• chemists commonly use two kinds
of arrows in reactions to indicate
the degree of completion of the
reactions
• a single arrow indicates all the
reactant molecules are converted to
product molecules at the end
• a double arrow indicates the
reaction stops when only some of
the reactant molecules have been
converted into products
  in these notes
 Strong or Weak
• a strong acid is a strong electrolyte
 practically all the acid molecules ionize, →
• a strong base is a strong electrolyte
 practically all the base molecules form OH– ions, either through
dissociation or reaction with water, →
• a weak acid is a weak electrolyte
 only a small percentage of the molecules ionize, 
• a weak base is a weak electrolyte
 only a small percentage of the base molecules form OH– ions,
either through dissociation or reaction with water, 
 Strong Acids
• The stronger the acid, the
more willing it is to donate H HCl  H+ + Cl-
HCl + H2O H3O+ + Cl-
 use water as the standard base
• strong acids donate
practically all their H’s
 100% ionized in water
 strong electrolyte
• [H3O+] = [strong acid]
 Weak Acids
• weak acids donate a small HF  H+ + F-
fraction of their H’s HF + H2O  H3O+ + F-
most of the weak acid
molecules do not donate H
to water
much less than 1% ionized
in water
• [H3O+] << [weak acid]
 Polyprotic Acids
• often acid molecules have more than one ionizable H –
these are called polyprotic acids
 the ionizable H’s may have different acid strengths or be equal
 1 H = monoprotic, 2 H = diprotic, 3 H = triprotic
 HCl = monoprotic, H2SO4 = diprotic, H3PO4 = triprotic
• polyprotic acids ionize in steps
 each ionizable H removed sequentially
• removing of the first H automatically makes removal of
the second H harder
 H2SO4 is a stronger acid than HSO4
 Acids Conjugate Bases
HClO4 ClO4-1
H2SO4 HSO4-1
HI I-1
HBr Br-1

Increasing Basicity
HCl Cl-1
HNO3 NO3-1
H3O+1 H2O
HSO4-1 SO4-2
H2SO3 HSO3-1
H3PO4 H2PO4-1
Increasing Acidity HNO2 NO2-1
HF F-1
HC2H3O2 C2H3O2-1
H2CO3 HCO3-1
H2S HS-1
NH4+1 NH3
HCN CN-1
HCO3-1 CO3-2
HS-1 S-2
H2O OH-1
CH3-C(O)-CH3 CH3-C(O)-CH2-1
NH3 NH2-1
CH4 CH3-1
OH-1 O-2
 Strengths of Acids & Bases
• commonly, acid or base strength is measured by
determining the equilibrium constant of a substance’s
reaction with water
HAcid + H2O  Acid-1 + H3O+1
Base: + H2O  HBase+1 + OH-1
• the farther the equilibrium position lies to the products,
the stronger the acid or base
• the position of equilibrium depends on the strength of
attraction between the base form and the H+
 stronger attraction means stronger base or weaker acid
 General Trends in Acidity
• the stronger an acid is at donating H, the
weaker the conjugate base is at accepting H
• higher oxidation number = stronger oxyacid
H2SO4 > H2SO3; HNO3 > HNO2
• cation stronger acid than neutral molecule;
neutral stronger acid than anion
H3O+1 > H2O > OH-1; NH4+1 > NH3 > NH2-1
base trend opposite
 Acid Ionization Constant, Ka
• acid strength measured by the size of the
equilibrium constant when react with H2O
HAcid + H2O  Acid-1 + H3O+1
• the equilibrium constant is called the acid
ionization constant, Ka
larger Ka = stronger acid

1 1
[Acid ]  [H 3O ]
Ka 
[HAcid]
Kesetimbangan asam basa :

HF + HNO2

HCOOH + CH3COOH
 Name Formula Ka1 Ka2 Ka3
Benzoic C6H5COOH 6.14 x 10-5
Propanoic CH3CH2COOH 1.34 x 10-5
Formic HCOOH 1.77 x 10-5
Acetic CH3COOH 1.75 x 10-5
Chloroacetic ClCH2COOH 1.36 x 10-5
Trichloroacetic Cl3C-COOH 1.29 x 10-4
Oxalic HOOC-COOH 5.90 x 10-2 6.40 x 10-5
Nitric HNO3 strong
Nitrous HNO2 4.6 x 10-4
Phosphoric H3PO4 7.52 x 10-3 6.23 x 10-8 2.2 x 10-13
Phosphorous H3PO3 1.00 x 10-2 2.6 x 10-7
Arsenic H3AsO4 6.0 x 10-3 1.05 x 10-7 3.0 x 10-12
Arsenious H3AsO3 6.0 x 10-10 3.0 x 10-14 very small
Perchloric HClO4 > 108
Chloric HClO3 5 x 102
Chlorous HClO2 1.1 x 10-2
Hypochlorous HClO 3.0 x 10-8
Boric H3BO3 5.83 x 10-10
Carbonic H2CO3 4.45 x 10-7 4.7 x 10-11
 Autoionization of Water
• Water is actually an extremely weak electrolyte
therefore there must be a few ions present
• about 1 out of every 10 million water molecules
form ions through a process called
autoionization
H2O  H+ + OH–
H2O + H2O  H3O+ + OH–
• all aqueous solutions contain both H3O+ and OH–
the concentration of H3O+ and OH– are equal in water
[H3O+] = [OH–] = 10-7M @ 25°C
When 1 out of every 10 million water molecules form ions
through a process called autoionization
H2O + H2O  H3O+ + OH–
Given: Initial 107 M [OH] = 1 [H+] = 1
Find: Kw
Concept Plan:
[H3O+] [OH]
Relationships: K w  [ H 3O ][OH - ]
Solution:
K w  [ H 3O  ][ OH- ]
Kw
[OH- ] 
[ H 3O  ]

Check: The units are correct. The fact that the

[H3O+] < [OH] means the solution is basic
 Ion Product of Water
• the product of the H3O+ and OH–
concentrations is always the same number
• the number is called the ion product of
water and has the symbol Kw
• [H3O+] x [OH–] = Kw = 1 x 10-14 at 25°C
if you measure one of the concentrations, you
can calculate the other
• as [H3O+] increases the [OH–] must
decrease so the product stays constant
inversely proportional
 Acidic and Basic Solutions
• all aqueous solutions contain both H3O+ and
OH– ions
• neutral solutions have equal [H3O+] and [OH–]
[H3O+] = [OH–] = 1 x 10-7
• acidic solutions have a larger [H3O+] than [OH–]
[H3O+] > 1 x 10-7; [OH–] < 1 x 10-7
• basic solutions have a larger [OH–] than [H3O+]
[H3O+] < 1 x 10-7; [OH–] > 1 x 10-7
 Example 15.2b – Calculate the [OH] at 25°C when the
[H3O+] = 1.5 x 10-9 M, and determine if the solution is
acidic, basic, or neutral
Given: [H3O+] = 1.5 x 10-9 M
Find: [OH]
Concept Plan:
[H3O+] [OH]
Relationships: K w  [ H 3O ][OH - ]
Solution:
K w  [ H 3O  ][ OH- ]
-] 1.0 1014 6
- K [OH  6.7  10 M
[OH ]  w
1.5 10 9
[ H 3O  ]
Check: The units are correct. The fact that the
[H3O+] < [OH] means the solution is basic
 Complete the Table
[H+] vs. [OH-]
[H+] 100 10-1 10-3 10-5 10-7 10-9 10-11 10-13 10-14
H+
H+
H+ H + H+

OH- OH- OH OH
- - OH-
[OH-]
 Complete the Table
+ -
[H ] vs. [OH ]
Acid Base
[H+] 100 10-1 10-3 10-5 10-7 10-9 10-11 10-13 10-14
H+
H+
H+ H + H +

OH OH OH
- - -
OH- OH-
[OH-]10-14 10-13 10-11 10-9 10-7 10-5 10-3 10-1 100
even though it may look like it, neither H+ nor OH- will ever be 0
the sizes of the H+ and OH- are not to scale
because the divisions are powers of 10 rather than units
 pH
• the acidity/basicity of a solution is often
expressed as pH
• pH = -log[H3O+], [H3O+] = 10-pH
exponent on 10 with a positive sign
pHwater = -log[10-7] = 7
need to know the [H+] concentration to find pH
• pH < 7 is acidic; pH > 7 is basic, pH = 7 is
neutral
 Sig. Figs. & Logs
• when you take the log of a number written in scientific
notation, the digit(s) before the decimal point come from
the exponent on 10, and the digits after the decimal
point come from the decimal part of the number
log(2.0 x 106) = log(106) + log(2.0)
= 6 + 0.30303… = 6.30303...
• since the part of the scientific notation number that
determines the significant figures is the decimal part,
the sig figs are the digits after the decimal point in
the log
log(2.0 x 106) = 6.30
 pH
• the lower the pH, the more acidic the solution; the
higher the pH, the more basic the solution
1 pH unit corresponds to a factor of 10 difference
in acidity
• normal range 0 to 14
pH 0 is [H+] = 1 M, pH 14 is [OH–] = 1 M
pH can be negative (very acidic) or larger than 14
(very alkaline)
pH of Common Substances
Substance pH
1.0 M HCl 0.0
0.1 M HCl 1.0
stomach acid 1.0 to 3.0
lemons 2.2 to 2.4
soft drinks 2.0 to 4.0
plums 2.8 to 3.0
apples 2.9 to 3.3
cherries 3.2 to 4.0
unpolluted rainwater 5.6
human blood 7.3 to 7.4
egg whites 7.6 to 8.0
milk of magnesia (sat’d Mg(OH)2) 10.5
household ammonia 10.5 to 11.5
1.0 M NaOH 14
 Example 15.3b – Calculate the pH at 25°C when the
[OH] = 1.3 x 10-2 M, and determine if the solution is
acidic, basic, or neutral
Given: [OH] = 1.3 x 10-2 M
Find: pH
Concept Plan:
[OH] [H3O+] pH

Relationships: K w  [ H 3O ][OH - ] pH  - log[H3O ]

Solution:
K w  [ H 3O  ][ OH- ] [H 3O ]  7.7 1013 M

[ H 3O  ] 
1.0  10 14

pH  - log 7.7 1013 
1.3  102 pH  12.11
Check: pH is unitless. The fact that the pH > 7 means the
solution is basic
 pOH
• another way of expressing the acidity/basicity of
a solution is pOH
• pOH = -log[OH], [OH] = 10-pOH
pOHwater = -log[10-7] = 7
need to know the [OH] concentration to find pOH
• pOH < 7 is basic; pOH > 7 is acidic, pOH = 7 is
neutral
 pH and pOH
Complete the Table
pH

[H+] 100 10-1 10-3 10-5 10-7 10-9 10-11 10-13 10-14
H+
H+
H+ H + H+

OH- OH-
[OH-]10-14 10-13 10-11 10-9
OH -
10-7
OH-
10-5 10-3
OH-
10-1 100

pOH
 pH and pOH
Complete the Table
pH 0 1 3 5 7 9 11 13 14

[H+] 100 10-1 10-3 10-5 10-7 10-9 10-11 10-13 10-14
H+
H+
H+ H + H+

OH- OH-
[OH-]10-14 10-13 10-11 10-9
OH -
10-7
OH-
10-5 10-3
OH-
10-1 100
pOH 14 13 11 9 7 5 3 1 0
 Relationship between pH and pOH
• the sum of the pH and pOH of a solution = 14.00
at 25°C
can use pOH to find pH of a solution

[ H 3O  ][OH - ]  K w  1.0  1014

 log [H O ][OH - ]   log 1.0  1014 
3

 log [H 3O ]   log [OH ]  14.00

 -
pH  pOH  14.00
 pK
• a way of expressing the strength of an acid or
base is pK
• pKa = -log(Ka), Ka = 10-pKa
• pKb = -log(Kb), Kb = 10-pKb
• the stronger the acid, the smaller the pKa
larger Ka = smaller pKa
because it is the –log
 Finding the pH of a Strong Acid
• there are two sources of H3O+ in an aqueous
solution of a strong acid – the acid and the water
• for the strong acid, the contribution of the water
to the total [H3O+] is negligible
shifts the Kw equilibrium to the left so far that
[H3O+]water is too small to be significant
except in very dilute solutions, generally < 1 x 10-4 M
• for a monoprotic strong acid [H3O+] = [HAcid]
for polyprotic acids, the other ionizations can
generally be ignored
• 0.10 M HCl has [H3O+] = 0.10 M and pH = 1.00
Tentukan pH larutan HCl 10-8 M

H2O  H+ + OH–

HCl → H+ + Cl-
 Finding the pH of a Weak Acid
• there are also two sources of H3O+ in and
aqueous solution of a weak acid – the acid and
the water
• however, finding the [H3O+] is complicated by
the fact that the acid only undergoes partial
ionization
• calculating the [H3O+] requires solving an
equilibrium problem for the reaction that defines
the acidity of the acid
HAcid + H2O  Acid + H3O+
 Ex 15.6 Find the pH of 0.200 M HNO2(aq)
solution @ 25°C
Write the reaction for
the acid with water
HNO2 + H2O  NO2 + H3O+
Construct an ICE
[HNO2] [NO2-] [H3O+]
table for the reaction
initial 0.200 0 ≈0
Enter the initial
concentrations – change
assuming the [H3O+] equilibrium
from water is ≈ 0

since no products initially, Qc = 0, and the reaction is proceeding forward

 Ex 15.6 Find the pH of 0.200 M HNO2(aq)
solution @ 25°C
HNO2 + H2O  NO2 + H3O+
represent the change
in the concentrations
[HNO2] [NO2-] [H3O+]
in terms of x initial 0.200 0 0
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.200 x x x
concentrations in
terms of x
Ka 
[NO-2 ][ H 3O ]

 x x 
substitute into the
equilibrium constant
HNO2  2.00  101  x 
expression
 Ex 15.6 Find the pH of 0.200 M HNO2(aq)
solution @ 25°C
Ka for HNO2 = 4.6 x 10-4
determine the value of
Ka from Table 15.5 [HNO2] [NO2-] [H3O+]
since Ka is very small, initial 0.200 0 ≈0
approximate the
change -x +x +x
[HNO2]eq = [HNO2]init
and solve for x 0.200x
equilibrium 0.200 x x


NO H O 
-


 xxxx 
x 4.6 10 2.00 10 
4 1
2.00  10  x 
2 3
Ka
HNO  2
1

2 x  9.6 103
4 x
4.6 10 
2.00 101
Ex 15.6 Find the pH of 0.200 M HNO2(aq)
solution @ 25°C
Ka for HNO2 = 4.6 x 10-4
check if the [HNO2] [NO2-] [H3O+]
approximation is
initial 0.200 0 ≈0
valid by seeing if x
< 5% of [HNO2]init change -x +x +x
equilibrium 0.200 x x
x = 9.6 x 10-3
3
9.6 10
1
100%  4.8%  5%
2.00 10
the approximation is valid
 Ex 15.6 Find the pH of 0.200 M HNO2(aq)
solution @ 25°C
Ka for HNO2 = 4.6 x 10-4
substitute x into the [HNO2] [NO2-] [H3O+]
equilibrium
initial 0.200 0 ≈0
concentration
definitions and solve change -x +x +x
equilibrium 0.200-x
0.190 x
0.0096 x
0.0096
x = 9.6 x 10-3
HNO2   0.200  x  0.200  9.6 103   0.190 M
NO  H O  x  9.6 10
-
2 3
 3
M
 Ex 15.6 Find the pH of 0.200 M HNO2(aq)
solution @ 25°C
Ka for HNO2 = 4.6 x 10-4
substitute [H3O+] [HNO2] [NO2-] [H3O+]
into the formula for
initial 0.200 0 ≈0
pH and solve
change -x +x +x
equilibrium 0.190 0.0096 0.0096


pH  -log H 3O 


  log 9.6 10 3
  2.02
 Ex 15.6 Find the pH of 0.200 M HNO2(aq)
solution @ 25°C
Ka for HNO2 = 4.6 x 10-4
check by substituting [HNO2] [NO2-] [H3O+]
the equilibrium
initial 0.200 0 ≈0
concentrations back into
the equilibrium constant change -x +x +x
expression and equilibrium 0.190 0.0096 0.0096
comparing the calculated
Ka to the given Ka
Ka 
NO H O 
2
-
3


though not exact, HNO2 
the answer is
reasonably close 
9.6  10 
3 2
 4.9  104
0.190
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2?
(Ka = 1.4 x 10-5 @ 25°C)
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2?
Write the reaction for HC H NO + H O  C H NO  + H O+
6 4 2 2 6 4 2 3
the acid with water
Construct an ICE [HA] [A-] [H3O+]
table for the reaction initial 0.012 0 ≈0
Enter the initial change
concentrations –
equilibrium
assuming the [H3O+]
from water is ≈ 0
Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2?
HC6H4NO2 + H2O  C6H4NO2 + H3O+
represent the change
in the concentrations
[HA] [A-] [H3O+]
in terms of x initial 0.012 0 0
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.012 x x x
concentrations in
terms of x
Ka 
[C6 H 4 NO-2 ][ H 3O ]

 x x 
substitute into the HC6H 4 NO2  1.2  102  x 
equilibrium constant
expression
 Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2? Ka = 1.4 x 10-5 @ 25°C
HC6H4NO2 + H2O  C6H4NO2 + H3O+
determine the value of
Ka [HA] [A2-] [H3O+]
since Ka is very small, initial 0.012 0 ≈0
approximate the change -x +x +x
[HA]eq = [HA]init and
solve for x 0.012x
equilibrium 0.012 x x


A H O 
-


xxxx  x 1.4 10 1.2 10 
5 2
1.2 10  x
Ka 3
HA 2

2 x  4.110 4
5 x
1.4 10 
1.2 102
 Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2? Ka = 1.4 x 10-5 @ 25°C
Ka for HC6H4NO2 = 1.4 x 10-5
check if the [HA] [A2-] [H3O+]
approximation is
initial 0.012 0 ≈0
valid by seeing if
x < 5% of change -x +x +x
[HC6H4NO2]init equilibrium 0.012 x x
x = 4.1 x 10-4
4
4.110
2
100%  3.4%  5%
1.2 10
the approximation is valid
 Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2? Ka = 1.4 x 10-5 @ 25°C

[HA] [A2-] [H3O+]

substitute x into the
equilibrium initial 0.012 0 ≈0
concentration change -x +x +x
definitions and solve
equilibrium 0.012-x x x
x = 4.1 x 10-4

HC H NO   0.012  x  0.012  4.110   0.012 M

6 4 2
4

C H NO  H O  x  4.110
6 4
-
2 3
 4
M
 Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2? Ka = 1.4 x 10-5 @ 25°C

[HA] [A2-] [H3O+]

substitute [H3O+]
into the formula for initial 0.012 0 ≈0
pH and solve change -x +x +x
equilibrium 0.012 0.00041 0.00041


pH  -log H 3O 


  log 4.110 4
  3.39
 Practice - What is the pH of a 0.012 M solution of
nicotinic acid, HC6H4NO2? Ka = 1.4 x 10-5 @ 25°C

check by substituting [HA] [A2-] [H3O+]

the equilibrium
initial 0.012 0 ≈0
concentrations back into
the equilibrium constant change -x +x +x
expression and equilibrium 0.012 0.00041 0.00041
comparing the calculated
Ka to the given Ka
[C 6 H 4 NO-2 ][ H 3O  ]
Ka 
the values match
HC 6 H 4 NO2 

4.1  10 
4 2
 1.4  10 5

1.2  10 
2
 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Write the reaction for
the acid with water
HClO2 + H2O  ClO2 + H3O+
Construct an ICE
[HClO2] [ClO2-] [H3O+]
table for the reaction
initial 0.100 0 ≈0
Enter the initial
concentrations – change
assuming the [H3O+] equilibrium
from water is ≈ 0
 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Ka for HClO2 = 1.1 x 10-2
represent the change [HClO2] [ClO2-] [H3O+]
in the concentrations
in terms of x
initial 0.100 0 ≈0
change -x +x +x
sum the columns to
find the equilibrium equilibrium 0.100-x x x
concentrations in
terms of x
Ka 
[ClO -2 ][ H 3O ]

 x x 
substitute into the
equilibrium constant
HClO 2  1.00  101  x 
expression
 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Ka for HClO2 = 1.1 x 10-2
determine the value of
Ka from Table 15.5 [HClO2] [ClO2-] [H3O+]
since Ka is very small, initial 0.100 0 ≈0
approximate the change -x +x +x
[HClO2]eq = [HClO2]init
and solve for x equilibrium 0.100-x x x

ClO H O   x x 

  
- 
  x  1.1102 1.00 101
1.00  10 
2 3
Ka
HClO 2
1

2 x  3.3 102
2 x
1.110 
1.00 101
 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Ka for HClO2 = 1.1 x 10-2
check if the [HClO2] [ClO2-] [H3O+]
approximation is initial 0.100 0 ≈0
valid by seeing if x
< 5% of [HNO2]init change -x +x +x
equilibrium 0.100-x x x

x = 3.3 x 10-2
2
3.3 10
1
100%  33%  5%
1.00 10
the approximation is invalid
 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Ka for HClO2 = 1.1 x 10-2
if the approximation

ClO H O 
-


x x 
1.00  10  x
2 3
Ka
is invalid, solve for x HClO 2  1

using the quadratic

2 x2
1.110 
1.00 10 
formula
1
x

0  x 2  0.011x  0.0011
 0.011  0.0112  4(1)(0.0011)
x
2(1)
x  0.028 or - 0.039
 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Ka for HClO2 = 1.1 x 10-2
substitute x into the [HClO2] [ClO2-] [H3O+]
equilibrium
concentration
initial 0.100 0 ≈0
definitions and solve change -x +x +x
equilibrium 0.100-x
0.072 0.028
x 0.028
x

x = 0.028
HClO 2   0.100  x  0.100  0.028  0.072 M
ClO  H O  x  0.028 M
-
2 3

 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Ka for HClO2 = 1.1 x 10-2
substitute [H3O+] [HClO2] [ClO2-] [H3O+]
into the formula for initial 0.100 0 ≈0
pH and solve
change -x +x +x
equilibrium 0.072 0.028 0.028


pH  -log H3O 

  log 0.028  1.55
 Ex 15.7 Find the pH of 0.100 M HClO2(aq)
solution @ 25°C
Ka for HClO2 = 1.1 x 10-2
check by substituting [HClO2] [ClO2-] [H3O+]
the equilibrium
concentrations back into
initial 0.100 0 ≈0
the equilibrium constant change -x +x +x
expression and equilibrium 0.072 0.028 0.028
comparing the calculated
Ka to the given Ka
Ka 
ClO H O 
-
2 3



the answer matches HClO 2 


0.028
2
 1.1  102
0.072 
 Ex 15.8 - What is the Ka of a weak acid if a
0.100 M solution has a pH of 4.25?
Use the pH to find the
equilibrium [H3O+] [H 3O  ]  10-pH  10 4.25  5.6 10 5 M
Write the reaction for HA + H2O  A + H3O+
the acid with water
Construct an ICE table [HA] [A-] [H3O+]
for the reaction initial 0.100 0 ≈0
Enter the initial change
concentrations and
[H3O+]equil equilibrium 5.6E-05
 Ex 15.8 - What is the Ka of a weak acid if a
0.100 M solution has a pH of 4.25?
HA + H2O  A + H3O+
fill in the rest of the
table using the
[HA] [A-] [H3O+]
[H3O+] as a guide initial 0.100 0 0
change −5.6E-05 +5.6E-05 +5.6E-05
if the difference is
insignificant, 0.100 
equilibrium 0.100 5.6E-05 5.6E-05
[HA]equil = [HA]initial 5.6E-05

[A - ][ H 3O ] 5.6  105 5.6  105 

substitute into the Ka
expression and Ka  
compute Ka HA  0.100
Ka  3.1  108
 Percent Ionization
• another way to measure the strength of an acid is
to determine the percentage of acid molecules that
ionize when dissolved in water – this is called the
percent ionization
the higher the percent ionization, the stronger the acid
molarity of ionized acid
Percent Ionization   100%
initial molarity of acid
• since [ionized acid]equil = [H3O+]equil

[H 3O ]equil
Percent Ionization  100%
[HA] init
 Ex 15.9 - What is the percent ionization of a
2.5 M HNO2 solution?
Write the reaction for HNO2 + H2O  NO2 + H3O+
the acid with water
[HNO2] [NO2-] [H3O+]
Construct an ICE table
for the reaction initial 2.5 0 ≈0
Enter the Initial change x +x +x
Concentrations
equilibrium 2.5  x x x
Define the Change in
Concentration in
terms of x
Sum the columns to
define the Equilibrium
Concentrations
 Ex 15.9 - What is the percent ionization of a
2.5 M HNO2 solution?
Ka for HNO2 = 4.6 x 10-4
determine the value of
Ka from Table 15.5 [HNO2] [NO2-] [H3O+]
since Ka is very small, initial 2.5 0 ≈0
approximate the change -x +x +x
[HNO2]eq = [HNO2]init
and solve for x equilibrium 2.5-x ≈2.5 x x

x2
4.6 10 4 
Ka 
NO H O  x x 
-
2 3


2.5
HNO2  2.5
x 4.6 10 2.5
4

x  3.4 10 2
 Ex 15.9 - What is the percent ionization of a
2.5 M HNO2 solution?
HNO2 + H2O  NO2 + H3O+
substitute x into the
Equilibrium [HNO2] [NO2-] [H3O+]
Concentration initial 2.5 0 ≈0
definitions and solve
change -x +x +x
x = 3.4 x 10-2
equilibrium x
2.52.5 0.034
x 0.034
x

HNO2   2.5  x  2.5  0.034  2.5 M

NO  H O  x  0.034 M
-
2 3

 Ex 15.9 - What is the percent ionization of a
2.5 M HNO2 solution?
HNO2 + H2O  NO2 + H3O+
Apply the Definition
and Compute the [HNO2] [NO2-] [H3O+]
Percent Ionization initial 2.5 0 ≈0
change -x +x +x
equilibrium 2.5 0.034 0.034
since the percent [H 3O  ]equil
ionization is < 5%, Percent Ionization  100%
[HNO 2 ]init
the “x is small”
approximation is 3.4 102
 100%  1.4%
valid 2.5
 Relationship Between
[H3O+]equilibrium & [HA]initial
• increasing the initial concentration
of acid results in increased H3O+
concentration at equilibrium Percent Ionization
• increasing the initial concentration 
[H O
of acid results in decreased percent  3 ]equil 100%
ionization [HA] init
• this means that the increase in H3O+
concentration is slower than the
increase in acid concentration
 Why doesn’t the increase in H3O+
keep up with the increase in HA?
• the reaction for ionization of a weak acid is:
HA(aq) + H2O(l)  A−(aq) + H3O+(aq)
• according to Le Châtelier’s Principle, if we reduce the
concentrations of all the (aq) components, the equilibrium
should shift to the right to increase the total number of
dissolved particles
 we can reduce the (aq) concentrations by using a more dilute
initial acid concentration
• the result will be a larger [H3O+] in the dilute solution
compared to the initial acid concentration
• this will result in a larger percent ionization
Finding the pH of Mixtures of Acids
• generally, you can ignore the contribution of the
weaker acid to the [H3O+]equil
• for a mixture of a strong acid with a weak acid, the
complete ionization of the strong acid provides more
than enough [H3O+] to shift the weak acid equilibrium
to the left so far that the weak acid’s added [H3O+] is
negligible
• for mixtures of weak acids, generally only need to
consider the stronger for the same reasons
 as long as one is significantly stronger than the other, and
their concentrations are similar
 Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO(aq)
Write the reactions for HF + H2O  F + H3O+ Ka = 3.5 x 10-4
the acids with water
and determine their Kas HClO + H2O  ClO + H3O+ Ka = 2.9 x 10-8
If the Kas are H2O + H2O  OH + H3O+ Kw = 1.0 x 10-14
sufficiently different,
use the strongest acid to
construct an ICE table [HF] [F-] [H3O+]
for the reaction initial 0.150 0 ≈0
Enter the initial change
concentrations –
assuming the [H3O+] equilibrium
from water is ≈ 0
 Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO2(aq)

represent the change

in the concentrations
[HF] [F-] [H3O+]
in terms of x initial 0.150 0 0
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.150 x x x
concentrations in
terms of x
Ka 
- 
[F ][ H 3O ]

 x x 
substitute into the
equilibrium constant HF 1.50 101  x 
expression
 Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO2(aq)
Ka for HF = 3.5 x 10-4
determine the value of
Ka for HF [HF] [F-] [H3O+]
since Ka is very small, initial 0.150 0 ≈0
approximate the
change -x +x +x
[HF]eq = [HF]init and
solve for x 0.150x
equilibrium 0.150 x x
F H O 
- 
xxxx 
 
3.5 10 1.50 10 
3
Ka
HF 0.150  x  x 4 1

4 x 2 x  7.2 103
3.5 10 
1.50 101
 Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO2(aq)
Ka for HF = 3.5 x 10-4
check if the [HF] [F-] [H3O+]
approximation is
initial 0.150 0 ≈0
valid by seeing if x
< 5% of [HF]init change -x +x +x
equilibrium 0.150 x x
x = 7.2 x 10-3
3
7.2 10
1
100%  4.8%  5%
1.50 10
the approximation is valid
 Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO2(aq)
Ka for HF = 3.5 x 10-4
substitute x into the [HF] [F-] [H3O+]
equilibrium
initial 0.150 0 ≈0
concentration
definitions and solve change -x +x +x
equilibrium 0.150-x
0.143 x
0.0072 x
0.0072
x = 7.2 x 10-3
HF  0.150  x  0.150  7.2 103   0.143 M
F  H O  x  7.2 10
-
3
 3
M
 Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO2(aq)
Ka for HF = 3.5 x 10-4
substitute [H3O+] [HF] [F-] [H3O+]
into the formula for
initial 0.150 0 ≈0
pH and solve
change -x +x +x
equilibrium 0.143 0.0072 0.0072


pH  -log H 3O 


  log 7.2 10 3
  2.14
 Ex 15.10 Find the pH of a mixture of 0.150 M
HF(aq) solution and 0.100 M HClO2(aq)
Ka for HF = 3.5 x 10-4
check by substituting [HF] [F-] [H3O+]
the equilibrium
initial 0.150 0 ≈0
concentrations back into
the equilibrium constant change -x +x +x
expression and equilibrium 0.143 0.0072 0.0072
comparing the calculated
Ka to the given Ka
Ka 
F H O 
-
3



though not exact, HF

the answer is
reasonably close 
7.2  10  3 2
 3.6  104
0.143
 Polyprotic Acids
• since polyprotic acids ionize in steps, each H has a
separate Ka
• Ka1 > Ka2 > Ka3
• generally, the difference in Ka values is great enough so
that the second ionization does not happen to a large
enough extent to affect the pH
 most pH problems just do first ionization
 except H2SO4  use [H2SO4] as the [H3O+] for the second
ionization
• [A2-] = Ka2 as long as the second ionization is negligible
 Ex 15.18 Find the pH of 0.0100 M H2SO4(aq)
solution @ 25°C
Write the reactions H2SO4 + H2O  HSO4 + H3O+
for the acid with
water HSO4 + H2O  SO42 + H3O+
Construct an ICE
[HSO4 ] [SO42 ] [H3O+]
table for the reaction
initial 0.0100 0 0.0100
Enter the initial
concentrations – change
assuming the equilibrium
[HSO4−] and [H3O+]
is ≈ [H2SO4]
 Ex 15.18 Find the pH of 0.0100 M H2SO4(aq)
solution @ 25°C
represent the change [HSO4 ] [SO42 ] [H3O+]
in the concentrations
in terms of x
initial 0.0100 0 0.0100
change −x +x +x
sum the columns to
find the equilibrium equilibrium 0.0100 −x x 0.0100 +x
concentrations in
[SO24- ][ H 3O ] x 0.0100  x 
terms of x Ka  
substitute into the [ HSO 4 ]-
0.0100  x 
equilibrium constant
expression

[H+] = 0.0200 M, pH = 1.699

 Ex 15.18 Find the pH of 0.0100 M H2SO4(aq)
solution @ 25°C
Ka for HSO4− = 0.012
expand and solve for [SO24- ][ H 3O ] x 0.0100  x 
Ka  
x using the quadratic
[ HSO 4 ]-
0.0100  x 
formula
0.012 
0.0100  x x
0.0100  x 
1.2  10  4  1.2  10  2 x  1.00  10  2 x  x 2
0  x 2  0.022 x  0.00012
 0.022  0.022 2  4(1)(0.00012 )
x
2(1)
x  0.027 or 0.0045
 Ex 15.18 Find the pH of 0.0100 M H2SO4(aq)
solution @ 25°C
Ka for HSO4− = 0.012
substitute x into the [HSO4 ] [SO42 ] [H3O+]
equilibrium
concentration
initial 0.0100 0 0.0100
definitions and solve change −x +x +x
0.0055−x 0.0045
equilibrium 0.0100 x 0.0145−x
0.0100

x = 0.0045
[HSO4 ]  0.0100  x  0.0100  0.0045   0.0055 M
[H3O ]  0.0100  x   0.0145 M


[SO 24- ]  x  0.0045 M

 Ex 15.18 Find the pH of 0.0100 M H2SO4(aq)
solution @ 25°C
Ka for HSO4− = 0.012
substitute [H3O+] [HSO4 ] [SO42 ] [H3O+]
into the formula for
pH and solve
initial 0.0100 0 0.0100
change −x +x +x
equilibrium 0.0055 0.0045 0.0145

pH  -log H3O  

  log 0.0145   1.839
 Ka for HSO4− = 0.012
check by substituting [HSO4 ] [SO42 ] [H3O+]
the equilibrium
concentrations back
initial 0.0100 0 0.0100
into the equilibrium change −x +x +x
constant expression equilibrium 0.0055 0.0045 0.0145
and comparing the
calculated Ka to the
given Ka

SO H O 
2-



HSO 
4 3
Ka -
the answer matches 4


0.00450.0145
 1.2  102
0.0055
 Ex 15.19
Ascorbic acid, H2Asc, known as vitamin C, is a diprotic
acid (Ka1 = 1.0x10-5 and Ka2 = 5x10-12) found in citrus
fruit. Calculate the pH of 0.050 M H2Asc @ 25°C
 Since Ka1 >> Ka2, we can assume that the first
dissociation produces almost all the H3O+. Also,
since Ka1 is small, the amount of H2ASc that
dissociates can be neglected.

SOLUTION:

[HAsc-][H3O+]
H2Asc(aq) + H2O(l) HAsc-(aq) + H3 O+(aq) Ka1 = = 1.0x10-5
[H2Asc]
[Asc2-][H3O+]
HAsc-(aq) + H2O(l) Asc2-(aq) + H3O+(aq) Ka2 = = 5x10-12
[HAsc-]
Concentration (M) H2Asc(aq) + H2O(l) HAsc-(aq) + H3O+(aq)
Initial 0.050 - 0 0
Change -x - +x +x
Equilibrium 0.050 - x - x x

[HAsc-][H3O+] x2 x2
Ka1 = -5
= 1.0x10 = ≈
[H2Asc] 0.050 - x 0.050

X = 7.1x10-4 M

x = [H3O+] = [Asc-] =

pH = -log[H3O+] = -log(7.1x10-4) = 3.15

 Strong Bases
• the stronger the base, the more
willing it is to accept H
use water as the standard acid
NaOH  Na+ + OH-
• for strong bases, practically all
molecules are dissociated into
OH– or accept H’s
strong electrolyte
multi-OH strong bases
completely dissociated
• [HO–] = [strong base] x (# OH)
Example 15.11b – Calculate the pH at 25°C of a 0.0015 M
Sr(OH)2 solution and determine if the solution is acidic,
basic, or neutral
Given: [Sr(OH)2] = 1.5 x 10-3 M
Find: pH
Concept Plan: [Sr(OH) ] [OH] [H3O+] pH
2
-
Relationships: [OH]=2[Sr(OH)2] K w  [ H 3O ][OH ] pH  - log[H3O ]


Solution:
K w  [ H 3O ][ OH- ]
 [H 3O ]  3.3 1012 M
[OH]
= 2(0.0015) [ H 3O  ] 
1.0  10 14

pH  - log 3.3 1012 
= 0.0030 M 3.0  103 pH  11.48
Check: pH is unitless. The fact that the pH > 7 means the
solution is basic
Practice - Calculate the pH of a 0.0010 M
Ba(OH)2 solution and determine if it is
acidic, basic, or neutral
Practice - Calculate the pH of a 0.0010 M
Ba(OH)2 solution and determine if it is
acidic, basic, or neutral
Ba(OH)2 = Ba2+ + 2 OH- therefore
[OH-] = 2 x 0.0010 = 0.0020 = 2.0 x 10-3 M
Kw = [H3O+][OH]
1.00 x 10 -14
[H3O+] = = 5.0 x 10 -12M
2.0 x 10-3
pH = -log [H3O+] = -log (5.0 x 10-12)
pH = 11.30
pH > 7 therefore basic
 Weak Bases
• in weak bases, only a small
fraction of molecules accept H’s
weak electrolyte NH3 + H2O  NH4+ + OH-
most of the weak base molecules
do not take H from water
much less than 1% ionization in
water
• [HO–] << [weak base]
• finding the pH of a weak base
solution is similar to finding the
pH of a weak acid
 Ex 15.12 Find the pH of 0.100 M NH3(aq) solution

Write the reaction for

the base with water
NH3 + H2O  NH4+ + OH
Construct an ICE
[NH3] [NH4+] [OH]
table for the reaction
initial 0.100 0 ≈0
Enter the initial
concentrations – change
assuming the [OH] equilibrium
from water is ≈ 0

since no products initially, Qc = 0, and the reaction is proceeding forward

Ex 15.12 Find the pH of 0.100 M NH3(aq) solution

represent the change

in the concentrations
[NH3] [NH4+] [OH]
in terms of x initial 0.100 0 0
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.100 x x x
concentrations in
terms of x
Kb 
[NH 4 ][OH  ]

 x x 
substitute into the
equilibrium constant
NH3  1.00  101  x 
expression
Ex 15.12 Find the pH of 0.100 M NH3(aq) solution
Kb for NH3 = 1.76 x 10-5
determine the value of
Kb from Table 15.8 [NH3] [NH4+] [OH]
since Kb is very small, initial 0.100 0 ≈0
approximate the
change -x +x +x
[NH3]eq = [NH3]init
and solve for x equilibrium 0.100
0.100 x x x


NH OH 


 xxxx 

 
x  1.76 105 1.00 101 
1.00 10  x 
44
K bb
NH  33
11

2 x  1.33 103
5 x
1.76 10 
1.00 101
Ex 15.12 Find the pH of 0.100 M NH3(aq) solution
Kb for NH3 = 1.76 x 10-5
check if the [NH3] [NH4+] [OH]
approximation is
initial 0.100 0 ≈0
valid by seeing if x
< 5% of [NH3]init change -x +x +x
equilibrium 0.100 x x
x = 1.33 x 10-3
3
1.33 10
1
100%  1.33%  5%
1.00 10
the approximation is valid
Ex 15.12 Find the pH of 0.100 M NH3(aq) solution
Kb for NH3 = 1.76 x 10-5
substitute x into the [NH3] [NH4+] [OH]
equilibrium
initial 0.100 0 ≈0
concentration
definitions and solve change -x +x +x
0.099x 1.33E-3
equilibrium 0.100 x x
1.33E-3
x = 1.33 x 10-3
NH3   0.100  x  0.100  1.33 10 3
  0.099 M
 3
[ NH4 ]  [OH ]  x  1.33 10
-
M
Ex 15.12 Find the pH of 0.100 M NH3(aq) solution
Kb for NH3 = 1.76 x 10-5
use the [OH-] to find [NH3] [NH4+] [OH]
the [H3O+] using Kw
initial 0.100 0 ≈0
substitute [H3O+]
change -x +x +x
into the formula for
pH and solve equilibrium 0.099 1.33E-3 1.33E-3

pH  -log H O 
K w  [H 3O  ][OH - ] 
3

  log 7.52 10   11.124

 1.00  10-14
[H 3O ]  12
1.33  10-3
[H 3O  ]  7.52  10-12
 Ex 15.12 Find the pH of 0.100 M NH3(aq) solution
Kb for NH3 = 1.76 x 10-5
check by substituting
the equilibrium [NH3] [NH4+] [OH]
concentrations back into initial 0.100 0 ≈0
the equilibrium constant
expression and change -x +x +x
comparing the calculated equilibrium 0.099 1.33E-3 1.33E-3
Kb to the given Kb

Kb 
NH OH 

4


though not exact, NH3 

1.33  10 
the answer is 3 2
reasonably close   1.8  105
0.099
 Acid-Base Properties of Salts
• salts are water soluble ionic compounds
• salts that contain the cation of a strong base and an
anion that is the conjugate base of a weak acid are
basic
 NaHCO3 solutions are basic
 Na+ is the cation of the strong base NaOH
 HCO3− is the conjugate base of the weak acid H2CO3
• salts that contain cations that are the conjugate acid of a
weak base and an anion of a strong acid are acidic
 NH4Cl solutions are acidic
 NH4+ is the conjugate acid of the weak base NH3
 Cl− is the anion of the strong acid HCl
 Anions as Weak Bases
• every anion can be thought of as the conjugate base of an
acid
• therefore, every anion can potentially be a base
 A−(aq) + H2O(l)  HA(aq) + OH−(aq)
• the stronger the acid is, the weaker the conjugate base is
 an anion that is the conjugate base of a strong acid is pH neutral
Cl−(aq) + H2O(l)  HCl(aq) + OH−(aq)
 since HCl is a strong acid, this equilibrium lies practically completely to the
left
 an anion that is the conjugate base of a weak acid is basic
F−(aq) + H2O(l)  HF(aq) + OH−(aq)
 since HF is a weak acid, the position of this equilibrium favors the right
Ex 15.13 - Use the Table to Determine if
the Given Anion Is Basic or Neutral
a) NO3−
the conjugate base of a
strong acid
NO2−
the conjugate base of a
weak acid
 Relationship between Ka of an Acid and
Kb of Its Conjugate Base
• many reference books only give tables of Ka values
because Kb values can be found from them
[ A  ][H 3O  ]
when you add  
HA( aq)  H 2O(l )  A ( aq)  H 3O ( aq) Ka 
[HA]
equations,
  [ HA][H 3O  ]
you multiply A ( aq)  H 2O(l )  HA( aq)  OH (aq) Kb 
[A  ]
the K’s
2 H 2O(l )  H3O (aq )  OH  (aq )

[A  ][ H 3O  ] [ HA ][ OH  ]
Ka  K b  
[ HA ] [A  ]
Ka  K b  [ H 3O  ][ OH  ]  K w
 Ex 15.14 Find the pH of 0.100 M
Na+ is the cation of a
strong base – pH NaCHO2(aq) solution
neutral. The CHO2−
is the anion of a CHO2− + H2O  HCHO2 + OH
weak acid – pH basic
[CHO2−] [HCHO2] [OH]
Write the reaction for
the anion with water initial 0.100 0 ≈0

Construct an ICE change

table for the reaction equilibrium
Enter the initial
concentrations –
assuming the [OH]
from water is ≈ 0
 Ex 15.14 Find the pH of 0.100 M NaCHO2(aq) solution
represent the change
in the concentrations [CHO2−] [HCHO2] [OH]
in terms of x initial 0.100 0 ≈0
sum the columns to change x +x +x
find the equilibrium
equilibrium 0.100 x x x
concentrations in
terms of x Ka  K b  K w
Calculate the value 1.0  1014 11
of Kb from the value Kb   5.6  10
1.8  104
of Ka of the weak
acid from Table 15.5
Kb 
[HCHO 2 ][OH  ]

x x 
substitute into the 
CHO2

 1.00  101  x 
equilibrium constant
expression
 Ex 15.14 Find the pH of 0.100 M NaCHO2(aq) solution
Kb for CHO2− = 5.6 x 10-11
since Kb is very small, [CHO2−] [HCHO2] [OH]
approximate the
− − initial 0.100 0 ≈0
[CHO2 ]eq = [CHO2 ]init
and solve for x change -x +x +x
0.100x
equilibrium 0.100 x x

Kbb 
[HCHO22][
[HCHO ][OHOH]]

 x xxx  x 2
K

CHO22
CHO

 11..00
0010 1011 x  5.6  10 11 
1.00  10 1

x 5.6 10 1.00 10 

11 1

x  2.4  10  6
Ex 15.14 Find the pH of 0.100 M NaCHO2(aq) solution
Kb for CHO2− = 5.6 x 10-11
[CHO2−] [HCHO2] [OH]
check if the initial 0.100 0 ≈0
approximation is
change -x +x +x
valid by seeing if x
< 5% of [CHO2−]init equilibrium 0.100 x x

x = 2.4 x 10-6
6
2.4  10
1
 100 %  0.0024 %  5%
1.00  10
the approximation is valid
 Ex 15.14 Find the pH of 0.100 M NaCHO2(aq) solution
Kb for CHO2− = 5.6 x 10-11
[CHO2−] [HCHO2] [OH]
substitute x into the initial 0.100 0 ≈0
equilibrium
change -x +x +x
concentration
definitions and solve 0.100−x
equilibrium 0.100 x
2.4E-6 x
2.4E-6

x = 2.4 x 10-6
CHO  0.100  x  0.100  2.4 10   0.100 M
2
 6

6
[HCHO 2 ]  [OH ]  x  2.4  10
-
M
 Ex 15.14 Find the pH of 0.100 M NaCHO2(aq) solution
Kb for CHO2− = 5.6 x 10-11
use the [OH-] to find [CHO2−] [HCHO2] [OH]
the [H3O+] using Kw
initial 0.100 0 ≈0
substitute [H3O+]
change -x +x +x
into the formula for
pH and solve equilibrium 0.100 2.4E-6 2.4E-6

K w  [H 3O  ][OH - ]
pH  -log H3O 

   8.38
 1.00  10 -14
[H 3O ]  9
2.4  10-6   log 4.2  10
[H 3O  ]  4.2  10-9
 Ex 15.14 Find the pH of 0.100 M NaCHO2(aq) solution
Kb for CHO2− = 5.6 x 10-11
check by substituting
[CHO −] [HCHO ] [OH]
the equilibrium 2 2
concentrations back into initial 0.100 0 ≈0
the equilibrium constant
expression and change -x +x +x
comparing the calculated equilibrium 0.100 2.4E-6 2.4E-6
Kb to the given Kb
HCHO 2 OH  

though not exact,
Kb
CHO  2


2.4  10 
the answer is 6 2
reasonably close   5.8  1011
0.100
 Contoh 7.5
Perkirakan apakah larutan garam berikut ini bersifat netral,
asam ataukah basa.
A. KCl B. KCN C. NH4I

Penyelesaian
A. KCl akan terurai menjadi kation K+ dan anion Cl- yang merupakan
asam dan basa lemah, sehingga tidak bereaksi dengan air maka
bersifat netral (tidak terhidrolisis)
B. KCN akan terurai menjadi kation K+ yang merupakan asam lemah
dan dan anion CN- sebagai basa kuat yang bereaksi dengan air
menghasilkan OH- sehingga larutan garam bersifat basa.
C. NH4I akan terurai menjadi kation NH4+ yang merupakan asam kuat,
NH4+ sehingga akan memberikan H+ pada air dan larutan garam
bersifat asam

143
Contoh 7.6
Hitunglah pH larutan
a. KCl 0,1 M b. KCN 0,1 M (Ka=4,9 x 10-10)
c. NH4CN 0,1 M (Kb=1,8 x 10-5)

Penyelesaian

a.KCl, garam akan menghasilkan asam dan basa lemah, pH = 7

b.[H+] = Kw.Ka/Cg = 10-14x(4,9x10-10/0,1) = 7x10-12
pH = 11,16

c. [H+] = Kw.Ka/Kb = 10-14x(4,9x10-10/1,8x10-5) = 3,59x10-10

pH = 9,63

144
Contoh 7.7
Hitunglah:
a. Ka larutan asam lemah pH 5,2 dengan konsentrasi 0,01M
b. Kb larutan basa lemah pH 9,0 dengan konsentrasi 0,01M
c. Ka asam lemah (HA) jika garam NaA 0,01M pH-nya 8,5
d. Kb basa lemah (MOH) jika garam MNO3 0,01M pH-nya 5,3

Penyelesaian
a.pH = 5,2; [H+] = 10-5,2; Ka = [H+]2/Ca = (10-5,2)2/0,01 = 4x10-9
b.pH = 9,0 maka pOH = 14 – 9 = 5; [OH-] = 10-5
Kb = [OH-]2/Cb = (10-5)2/0,01 = 1x10-8
c. pH = 8,5; [H+] = 10-8,5; Ka = [H+]2.Cg/Kw
= (10-8,5)2 x 0,01/10-14 = 10-5
d. pH = 5,3; [H+] = 10-5,3; Kb = Cg.Kw/[H+]2
= 0,01 x 10-14/(10-5,3)2 = 4x10-6 145
 Classifying Salt Solutions as
Acidic, Basic, or Neutral
• if the salt cation is the counterion of a strong
base and the anion is the conjugate base of a
strong acid, it will form a neutral solution
NaCl Ca(NO3)2 KBr
• if the salt cation is the counterion of a strong
base and the anion is the conjugate base of a
weak acid, it will form a basic solution
NaF Ca(C2H3O2)2 KNO2
 Classifying Salt Solutions as
Acidic, Basic, or Neutral
• if the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
strong acid, it will form an acidic solution
NH4Cl
• if the salt cation is a highly charged metal ion
and the anion is the conjugate base of a strong
acid, it will form an acidic solution
Al(NO3)3
 Classifying Salt Solutions as
Acidic, Basic, or Neutral
• if the salt cation is the conjugate acid of a weak
base and the anion is the conjugate base of a
weak acid, the pH of the solution depends on the
relative strengths of the acid and base
NH4F since HF is a stronger acid than NH4+, Ka of
NH4+ is larger than Kb of the F−; therefore the
solution will be acidic
 Strengths of Binary Acids
• the more d+ H-X d- polarized the
bond, the more acidic the bond
• the stronger the H-X bond, the
weaker the acid
• binary acid strength increases to the
right across a period
 H-C < H-N < H-O < H-F
• binary acid strength increases down
the column
 H-F < H-Cl < H-Br < H-I
 Strengths of Oxyacids, H-O-Y
• the more electronegative the Y atom, the
stronger the acid
helps weakens the H-O bond
• the more oxygens attached to Y, the stronger the
acid
further weakens and polarizes the H-O bond
 Lewis Acid - Base Theory
• electron sharing
• electron donor = Lewis Base = nucleophile
must have a lone pair of electrons
• electron acceptor = Lewis Acid = electrophile
electron deficient
• when Lewis Base gives electrons from lone
pair to Lewis Acid, a covalent bond forms
between the molecules
 Example - Complete the Following
Lewis Acid-Base Reactions
Label the Nucleophile and Electrophile
OH
+ OH-1 
H C H

OH OH
•• -1 
H C H + •• OH
••
H C H
 Basa
Asam
OH
 Lewis Acids & Bases
• Species that do not contain Hydrogen
++
in their
formulas, such as CO2 and Cu function as
Lewis acids by accepting an electron pair
• The donated proton of a Bronsted-Lowry acid
acts as a Lewis acid by accepting an electron pair
donated by the base:
 The Lewis acids are Yellow and the Lewis bases are
Blue in following reaction
BF3 + :NH3  BF3NH3
Fe3+ + 6 H2O  Fe(H2O)63+
HF + H2O  F- + H3O+

d+ d-
5/1/2019 153
 Lewis Acids & Bases
• Molecules as Lewis Acids
 Lewis Acids with Electron-Deficient atoms
 Molecular Lewis acids contain a central atom that
is electron deficient – valence shell incomplete (< 8
e-)
 Group 3A elements, such as Boron & Aluminum
react to complete the octet
F F
H
H
B + N
B N
F HH F
F F HH

An acid is an A base is an
electron-pair electron-pair
acceptor donor
5/1/2019 154
 Lewis Acids & Bases
• Solubility Effects
 A Lewis acid-base reaction between nonpolar
diethyl ether and normally insoluble Aluminum
Chloride

d-
d+

 The solubility of Aluminum chloride in dimethyl ether

results from the Oxygen acting as a base by donating an
electron pair to the Aluminum acting as an acid forming a
polar covalent bond

5/1/2019 155
 Practice - Complete the Following
Lewis Acid-Base Reactions

• BF3 + HF 

• CaO + SO3 

• KI + I2 
 Practice - Complete the Following
Lewis Acid-Base Reactions

• BF3 + HF  H+1BF4-1 F F
-1
Ele Nuc ••
H F +B F H+1 F B F

••
c ••
F F
• CaO + SO3  Ca+2SO4-2 O
Nuc Elec O -2
••
Ca+2 O -2
••
••
+S O Ca+2 O S O
••
• KI + I2  KI3 O O
Nuc Elec ••
K+1 -1 + I I K+1 I I I -1
••

I
••

••
 What Is Acid Rain?
• natural rain water has a pH of 5.6
naturally slightly acidic due mainly to CO2
• rain water with a pH lower than 5.6 is called
acid rain
• acid rain is linked to damage in ecosystems and
structures
 What Causes Acid Rain?
• many natural and pollutant gases dissolved in the air
are nonmetal oxides
 CO2, SO2, NO2
• nonmetal oxides are acidic
CO2 + H2O  H2CO3
2 SO2 + O2 + 2 H2O  2 H2SO4
• processes that produce nonmetal oxide gases as waste
increase the acidity of the rain
 natural – volcanoes and some bacterial action
 man-made – combustion of fuel
• weather patterns may cause rain to be acidic in regions
other than where the nonmetal oxide is produced
 Damage from Acid Rain
• acids react with metals, and materials that contain
carbonates
• acid rain damages bridges, cars, and other metallic
structures
• acid rain damages buildings and other structures made
of limestone or cement
• acidifying lakes affecting aquatic life
• dissolving and leaching more minerals from soil
 making it difficult for trees