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Acids and Bases II:
Acid-Base Equilbria
Acids and Bases: Chem 16 • Arrhenius Definition
OHOH + H l2-(aq)(aq)
• ACIDS – donates H+
• HNO3, H3PO4, H2SO4, HCl, HI, HBr, CH3COOH, organic-COOH, H2SO3
• BASES – donates OH-
• NaOH, KOH, LiOH, CsOH, Mg(OH)2,Sr(OH)2,Ba(OH)2 , Ca(OH)2
Acids and Bases: Chem 16 • Bronsted-Lowry Definition
4(aq)-(aq)3(g)(l)2 NHOH NH OH
• ACIDS – donates H+ • (proton donor)
• HNO3, H3PO4, H2SO4, HCl, HI, HBr, CH3COOH, organic-COOH, H2SO3
• BASES – accepts H+ • (proton acceptor)
• NH3, organic-NH2, NaOH, KOH, LiOH, CsOH, Mg(OH)2,Sr(OH)2,Ba(OH)2 , Ca(OH)2
Acids and Bases: Chem 16 • Bronsted-Lowry Definition
Acids and Bases: Chem 16 • Amphoterism:
– Species that can behave as an acid or base are called amphoteric.
– Proton transfer reactions in which a species behaves as either an acid or base is called amphiprotic
OH 2 ) Zn(NO HNO 2 Zn(OH) 22332 -2
4-
2 Zn(OH)OH 2 Zn(OH)
HPO43- + H2O H2PO4
2- + OH-
HPO43- + H2O PO4
3- + H3O+
Acids and Bases: Chem 16 • Lewis Definition
• ACIDS – electron-pair acceptor
• H+ (∴ all molecules with H+)• Electron deficient molecules
(below-octet atoms eg. Boron cmpds)
• BASES – electron-pair donor
• OH- (∴ all molecules with OH-)• Molecules with lone e- pairs
acid base
OH NH OH NH -423
base acid
BF Na BF NaF -43
Lewis
Brønsted-Lowry
Arrhenius
Hehehe...
Acids and Bases: Chem 16 17
• The Autoionization of water -
(aq)(aq)3)(2)(2 OHOHOH OH
Equilibrium-constant expression:2
2
-3
c ]O[H
]][OHOH[K
But concentration of water is constant (and large) at 25oC, therefore:
]][OHOH[K K -3wc
Experimental concentration H+ is determined to be 1.00x10-7 at 25oC, therefore: C25at 101.00x K
)10x 00.1)(10(1.00x Ko14-
w
-7-7w
Acids and Bases: Chem 16 17 pH = -log [H3O+] or simply –log[H+]pOH = -log[OH-]Kw = 1.00 x 10-14 = [H+][OH-] at 25oC
∴ pOH + pH = 14.00
Proof:-log Kw = -log [1.00 x 10-14] = -log ([H+][OH-])-log Kw = 14.00 = -log[H+] + -log[OH]-
14.00 = pH + pOH
Acids and Bases: Chem 16 17 • Calculate the [H3O+], pH, [OH-], and pOH for a 0.020 M HNO3
solution.– Is HNO3 a weak or strong acid?
– What is the [H3O+] ?
70.1pH
100.2-logpH
100.2OH
0.020 0.020 020.0
NOOHOHHNO
2
23
-33
100%23
M
M
MMM
• What is pH of water at its normal boiling point? Is it acidic or basic?– Given: ∆Hf
oH2O(l) = -285.83 kJ/mol
∆Hfo
OH-(aq) = -230.0 kJ/mol
When concentration of acid reaches 1.00 x 10-5 and below, the [H+] of H2O should be added, where [H+] = 1.00 x 10-7 (only used at 25oC)
Example: What is the pH of a solution prepared by diluting 1.0 mL of 0.1 M HCl with 1000 liters of water?
Acids and Bases: Chem 16 • Relative Strengths of Acids and Bases
Conjugate Acid-Base Pairs The weaker the acid or base, the stronger the conjugate partner.
The stronger the acid or base, the weaker the conjugate partner.
2(g)(l)2(aq)32(aq)3(aq)3(aq)32
(aq)3(aq)(aq)(aq)3
COOHCOHOO2NaCHOOHCH2CONa
COOHCH NaCl HCl OONaCH
STRONGER ACID and BASE
WEAKER ACID and BASE
Ionization Constants for Monoprotic Weak Acids and Bases
• Consider an aqueous solution of acetic acid, CH3COOH. What is the equilibrium constant expression?
CH3COOH(aq) + H2O(l) ⇄ CH3COO-(aq) + H3O+
(aq)
]OCOOH][H[CH
]COO][CHOH[K
23
-33
c
But [H2O] = 55.6 M, very high and almost constant, therefore
COOH][CH
]COO][CHOH[KK
3
-33
ac
• Because of its simplified form, we can write the equation for dissociation as
CH3COOH(aq) ⇄ CH3COO-(aq) + H+
(aq)
COOH][CH
]COO][CHH[K
3
-3
a
COOH][CH
]COO][CHOH[KK
3
-33
ac
Ka is the acid-dissociation constant
• For weak bases,NH3(aq) + H2O(l) NH⇄ 4
+(aq) + OH-
(aq)
O]][H[NH
]][NHOH[K
23
4c
][NH
]][NHOH[K
3
4b
Kb is the base-dissociation constant. But why???Does the base dissociate, like acids?
[acid]
]base e][conjugatH[Ka
[base]
]acid e][conjugatOH[Kb
HA ⇄ H+ + A-
B- + H2O ⇄ OH- + BH
The ionization constant values for several acids are given below.◦ Which acid is the strongest?
Acid Formula Ka value
Acetic CH3COOH 1.8 x 10-5
Nitrous HNO2 4.5 x 10-4
Hydrofluoric HF 7.2 x 10-4
Hypochlorous HClO 3.5 x 10-8
Hydrocyanic HCN 4.0 x 10-10
Ionization Constants for Monoprotic Weak Acids and Bases
The order of increasing acid strength for these weak acids is:
HCN>HClO>COOHCH>HNO>HF 32
Calculate the concentrations of the various species in 0.15 M acetic acid, CH3COOH, solution.
ALWAYS write down the ionization reaction and the ionization constant expression.
5
3
-33
a
-3323
108.1COOHCH
COOCHOHK
COOCHOH OHCOOHCH
Ionization Constants for Monoprotic Weak Acids and Bases
xMxM-x)M.(
xMxMxM
M
150 ] [ mEquilibriu
- Change
0.15 ] [ Initial
COOCH OH OHCOOHCH -3323
• Short-cut: Use the simplfying assumption-
Since x << 0.15, assume that 0.15 – x ≈ 0.15
If Ka /[ ]initial is < 1.0x10-3 , the simplifying assumption is valid
Percent Ionization of Weak Acids/Bases
Calculate the percent ionization of 0.15 M acetic acid. The percent ionization of acetic acid is
%1.1%10015.0
106.1ionization %
%100COOHCH
Hor COOCH= ionization %
3
original3
-3
M
M
equilequil
Percent Ionization of Weak Acids/Bases
• Calculate the percent ionization of 0.15 M hydrocyanic acid, HCN. Ka = 4.0 x 10-10
– Compare the %ionization of HCN and HOAc.
Note that the [H+] (or %ionization) in 0.15 M acetic acid is 215 times greater than for 0.15 M HCN.
Solution Ka [H+] pH % ionization
0.15 M HOAc
1.8 x 10-5 1.6 x 10-3 2.80 1.1
0.15 M
HCN
4.0 x 10-10 7.7 x 10-6 5.11 0.0051
Solvolysis: Reaction of Acid/Base with solvent
• Solvolysis is the reaction of a substance with the solvent in which it is dissolved.
• Hydrolysis refers to the reaction of a substance with water or its ions.
• Combination of the anion of a weak acid with H3O+ ions from water to form nonionized weak acid molecules.
Solvolysis: Reaction of Acid/Base with solvent
• Consider the acid HA HA + H2O A⇄ - + H3O+ Ka
Reverse form: A- + H3O+ ⇄ HA + H2O Ka
’ = 1/Ka
• Consider the conjugate base, A-
A- + H2O HA + OH⇄ - Kb
Reverse form: HA + OH- A⇄ - + H2O Kb
‘ = 1/Kb
Solvolysis: Reaction of Acid/Base with solvent
• How is Ka related to Kb?
HA + H2O A⇄ - + H3O+ Ka
A- + H2O HA + OH⇄ - Kb
H2O + H2O ⇄ H3O+ + OH- Kw
baw K x KK a
wb K
KK
b
wa K
KK
The order of increasing acid strength for the weak acids is:
HCN>HClO>COOHCH>HNO>HF 32
The order of increasing base strength of the anions (conjugate bases) of the same acids is:
---3
-2
- CN<ClO<COOCH<NO<F
1.8 x 10-54.5 x 10-47.2 x 10-4 3.5 x 10-8 4.0 x 10-10
a
wb K
KK
5.6 x 10-101.4 x 10-112.2 x 10-11 2.9 x 10-7 2.5 x 10-5
The stronger the acid/base, the weaker is its conjugate
Strengths of Acids and Bases Strengths of BINARY Acids - acid strength increases with
decreasing H-X bond strength.
◦ VIIA hydrohalic acidsBond strength has this periodic trend
HF >> HCl > HBr > HIAcid strength has the reverse trend.
HF << HCl < HBr < HI◦ VIA hydrides.
Bond strength has this trend.H2O >> H2S > H2Se > H2Te
The acid strength is the reverse trend.H2O << H2S < H2Se < H2Te
Strengths of Acids and Bases
• Down a group: size, energy to break H- bond (electronegativity), acidity
Arrange in order of increasing acidity: NH3, OH2, HF
NH3 < OH2 < HF
(Electronegativity trend: NH3 < OH2 < HF)
• Across a period: electronegativity, acidity
Strengths of Acids and Bases
• TERNARY ACIDS - hydroxides of nonmetals that produce H3O+ in water.– Consist of H, O, and a nonmetal. HClO4 H3PO4
Strengths of Acids and Bases
• Acidity of ternary acids with same central element increase with increasing oxidation state of central element, and increasing O atomsHClO < HClO2 < HClO3 < HClO4
weakest strongest
Cl oxidation states +1 +3 +5 +7
Strengths of Acids and Bases
• ternary acids of the same group and same number of O atoms increase in acidity with increase electronegativity of central atom
H2SeO4 < H2SO4
HBrO4 < HClO4
HBrO3 < HClO3
However for phosphorus ternary acids: H3PO2 > H3PO3 > H3PO4 – relative position of H is important (based on structures only!)
Hard and Soft Acids and BasesFrom previous discussion, the STRENGTH of an
acid or a base depends on the value of its dissociation constant Ka or Kb, respectively
Hardness or Softness of an acid/base depends on POLARIZABILITY of molecule◦ Recall that “Polarizability“ is used in describing the
type of IMFA of molecules◦ The concept of Hardness or Softness of acids/bases is
Lewis-structure dependent, therefore it is a concept applied only in the LEWIS DEFINITION of acids/bases.
• More polarizable molecules (greater # of π e- or lone pairs) – SOFT Lewis acids/bases
• Less polarizable molecules – HARD Lewis acids/bases
HARD acid-HARD baseSOFT acid-SOFT base
>Dissociation constant
In general, molecules that involve
HARD acid-SOFT baseSOFT acid-HARD base
Hard Lewis acid
Which is the Hardest Lewis base? Which is the softest?
---3
-2
- CN ClO COOCH NO FHARDESTLewis base
SOFTESTLewis base
• In a 0.12 M solution of a weak monoprotic acid, HY, the acid is 5.0% ionized. Calculate the dissociation constant for the weak acid.
The pH of a 0.10 M solution of a weak monoprotic acid, HA, is found to be 2.97. What is the value of its dissociation constant?
Polyprotic Acids/Bases• Many weak acids contain two or more acidic hydrogens.
– Examples include H3PO4 and H3AsO4.
• The calculation of equilibria for polyprotic acids is done in a stepwise fashion.– There is a dissociation constant for each step
• Consider arsenic acid, H3AsO4, which has three ionization constants.1 Ka1 = 2.5 x 10-4
2 Ka2 = 5.6 x 10-8
3 Ka3 = 3.0 x 10-13
• Calculate the concentration of all species in 0.100 M arsenic acid, H3AsO4, solution.
You may apply the simplifying assumption in each step (1 ICE table/ dissociation)
11-a2(aq)3
-23(aq)(l)2
-3(aq)
-7a1(aq)3
-3(aq)(l)23(aq)2
10 x 4.7 K OH COOH HCO
10 x 4.4K OH + HCOOHCOH
8-b2(aq)3(aq)2(l)2
-3(aq)
-4b1(aq)
-3(aq)(l)2
-23(aq)
10 x 2.3 K HO COHOH HCO
10 x 1.2K HO + HCOOHCO
b2a2
w
b1a1
KK
K
KK
K HO POHOH POH
K HO POHOH HPO
K HO + HPOOHPO
b3(aq)4(aq)3(l)2-4(aq)2
b2(aq)-4(aq)2(l)2
-24(aq)
b1(aq)-2
4(aq)(l)2-3
4(aq)
b3a3
b2wa2
b1a1
KK
KKK
KK
13-a3(aq)3
-34(aq)(l)2
-24(aq)
8-a2(aq)3
-24(aq)(l)2
-4(aq)2
-3a1(aq)3
-4(aq)2(l)24(aq)3
10 x 3.60 K OH POOH HPO
10 x 6.20 K OH HPOOH POH
10 x 50.7K OH + POHOHPOH
• The behaviour of an amphiprotic species (acting as base or acid) depends on its dissociation constants
11-a2(aq)3
-23(aq)(l)2
-3(aq)
-8b2(aq)3(aq)2(l)2
-3(aq)
10 x 4.80 K OH COOH HCO
10 x 2.38 K OH COHOH HCO
12-b3(aq)4(aq)3(l)2
-4(aq)2
-8a2(aq)3
-24(aq)(l)2
-4(aq)2
10 x 1.33 K OH POHOH POH
10 x 6.20 K OH HPOOH POH
7-b2(aq)
-4(aq)2(l)2
-24(aq)
-13a3(aq)3
-34(aq)(l)2
-24(aq)
10 x 1.61 K OH POHOH HPO
10 x 3.6 K OH POOH HPO
• What is the pH of the resulting solution obtained by dissolving 1.52 g of NaH2PO4•2H2O in 50.00 mL water? If the salt added was Na2HPO4•2H2O instead, will the solution be basic or acidic?
• You accidentally spilled muratic acid (2.0 M HCl) on the rubber slippers of your room mate. To neutralize the acid, you looked for a base in your dorm stock room, and you found two salts – sodium bicarbonate and sodium phosphate. Which of the two salts will you use?
Inorganic Lewis Acids – Hydrolysis of Metal Ions
Because metal ions are positively charged, they attract the electrons of oxygen atoms in water.◦ Depending on the strength of electron interacting with
the cation, the water molecule can turn into hydroxide anion and release H+
◦ The acid strength of these ion-complexes acting as Lewis acids depend on size and charge of cation center
3-a(aq)
2(aq)52
3)aq(62 10 x 2.0 K H (OH)O)Fe(H )OFe(H
Na(NO3) Ca(NO3)2 Zn(NO3)2 Al(NO3)3 7.0 6.9 5.5 3.5
Salts of acids and bases Aqueous solutions of salts of strong acids and strong bases
are neutralExamples: NaCl (from HCl and NaOH)
K2SO4 (from KOH and H2SO4) Aqueous solutions of salts of strong bases and weak acids
are basicExamples: NaCN (from NaOH and HCN)
K2C2O4 (from KOH and H2C2O4) Aqueous solutions of salts of weak bases and strong acids
are acidicExamples: NH4Cl (from NH3 and HCl)
(CH3)3NHBr ((CH3)N and HBr)
How about – KHC2O4? NaHSO4? LiHSO3?
Salts of acids and bases• Aqueous solutions of salts of weak bases and weak acids
can be neutral, basic or acidic.The values of Ka and Kb determine the pH.
NH4CH3COO?
Compare Ka of NH4+ vs Kb of OAc-
MgNH4PO4?
Compare Ka of NH4+ and Mg2+ vs Kb of OAc-
NH4(HCO3)?
Compare Ka of NH4+ vs Kb/Ka of amphiprotic HCO3
-
Common Ion Effect and
Buffers/Buffer Capacity
Common Ion Effect – A special name for a Le Chatelier-based shift
• Consider a solution of 0.05 M acetic acid, CH3COOH (50.00 mL)
5-a(aq)3(aq)3)l(2(aq)3 10 x 1.8 K OH COOCH OH COOHCH
OH COOCH OH COOHCH (aq)3(aq)3)l(2(aq)3
OH COOCH OH COOHCH (aq)3(aq)3)l(2(aq)3
• Describe the direction of equilibrium shift
After adding 10.00 mL of 0.5 M HCl
After adding 10.00 mL of 0.5 M NaCH3COO
In COMMON-ION effect, the direction of shift of equilibrium is always towards the side that diminishes the added common/similar ion
Common Ion Effect – A special name for a Le Chatelier-based shift
• Consider a solution of 0.05 M acetic acid, CH3COOH (50.00 mL)
• Describe the pH of the final mixture– After adding 10.00 mL of 0.5 M HCl
– After adding 10.00 mL of 0.5 M NaCH3COO
DECREASE pH, more ACIDIC
INCREASE pH, less ACIDIC
Buffers• Solutions that contain BOTH acid component and
its conjugate base– Conjugate base is directly added, not the one calculated
from equilibrium– Examples :
• Acetic acid added with sodium acetate• Ammonium chloride added with aqueous ammonia solution
• Solutions that resist drastic pH changes
Henderson-Hasselbalch EquationSimplified equation for pH calculation involving
buffers
Buffers What is pH of a buffer that is 0.12 M in lactic acid, HC3H5O5,
and 0.10 M in sodium lactate?Ka = 1.40 x 10-4
The most important aspect of buffer solutions is that they resist drastic changes of pH upon adding strong acids or bases!
OH COOOHC OH COOHOHC (aq)3(aq)344)l(2(aq)344
0.10 M0.12 M
+ x + x - x
ICE 0.12 - x 0.10 + x x
(0.12)
(0.10) pK pH a
x) (0.12
x) (x)(0.10 K a
Common Ion Effect – Buffers• Non-buffer Case - Consider the a solution of 50.00 mL of 0.05 M acetic
acid, CH3COOH. Calculate the pH of the final mixture after adding 10.00 mL of 0.05 M HCl.
OH COOCH OH COOHCH (aq)3(aq)3)l(2(aq)3
Because HCl is a strong acid, it directly contributes to the initial concentration of H3O+ in the equilibrium calculation Set-up ICE table in MOLE basis, then convert to molarity when calculating/equating to Ka.
(10.00 mL) •(0.05 M)
(50.00 mL) •(0.05 M)
+ x + x - x
I
C
Common Ion Effect – Buffers• Buffer CASE - Consider a solution of 50.00 mL 0.05 M acetic acid
(CH3COOH) and 0.05 M sodium acetate (NaCH3COO). Calculate the pH of the final mixture after adding 10.00 mL of 0.05 M HCl.
Step 1: STOICHIOMETRIC calculation
Which has the lowest change in pH (∆pH)?
Try calculating the pH after adding 10.00 mL of 0.05 M NaOH (instead HCl) for the 2 cases.
Step 2: EQUILIBRIUM calculation, HH
mL) 60.00 volume(total
M) mL)(0.05 (60.00
mL) 60.00 volumetotal(
M) mL)(0.05 00.40(
log pKpH a
Henderson-Hasselbalch Equation
HA + H2O ⇄ A- + H3O+ B + H2O ⇄ BH+ + HO-
HH equation only used when salt is present – that is, present separately, not the [salt] from ICE calculation
The salt-component must be added separately, or generated by neutralizing the main component
In calculations involving buffers, ICE table must be in terms of MOLES especially if volumes are not same. However, equating with Ka must be in MOLARITY.
HH equation is allowed only when “simplifying assumptions” are valid
Preparation of BuffersBuffers can be prepared in three ways
◦ Adding a solid component to a liquid component Ex. NaCH3COO solid added to a solution of acetic acid (acetic-acetate
buffer)
◦ Neutralizing a liquid component with a strong opposite component Ex. Aqueous ammonia added with liquid HCl (ammonia-ammonium
buffer) Aqueous phosphoric acid added with solid NaOH (phosphate
buffer)
◦ Mixing two solid components in the same volume of water Ex. Solid NaH2PO4•H2O and solid Na2HPO4•7H2O dissolved in water
(phosphate buffer)
Preparation of Buffers
• How many grams of NH4Cl must be added to 2.0 L of 0.10 M NH3 to form a buffer of pH 9.00?
Kb NH3 = 1.8 x 10-5
What volume of 0.5 M NaOH must be added to 50 mL of 0.1 M benzoic acid (C6H5COOH) to make 100.0 mL of 0.05 M benzoate buffer that is pH 4.5?
Ka benzoic acid = 6.3 x 10-5
Preparation of Buffers• Prepare a 100.0 mL 0.1 M phosphate buffer, pH 8.00.
– Given:H3PO4 pKa1 = 2.12pKa2 = 7.21pKa3 = 12.38
Molarity H3PO4 (liquid) = 14.85 MFormula weightNaH2PO4•H2O = 137.99 g/moleNa2HPO4•7H2O = 268.07 g/mole
7.21 pK OH HPOOH POH a2(aq)3-2
4(aq)(l)2-4(aq)2
)POH (moles
)HPO (moleslog pK pH
-42
-24
a2
componentsbuffer moles totalHPO moles POH moles -24
-42
M) (0.1)L 1
mL 1000(
mL) (100.0 HPO moles POH moles -2
4-42
Buffer Capacity
Amount of acid or base (usually in mL) needed to change the pH of a buffer solution by 1 degree.
Compare the two buffers:- 100 mL of 1.0 M NaCH3COO and 1.0 M CH3COOH
- 100 mL of 0.1 M NaCH3COO and 0.1 M CH3COOH
- Which has the highest buffer capacity relative to 1.0 M NaOH?
Acid-Base Neutralizations:Indicators, Titrations
andpH curves
Acid-Base Indicators
• The point at which chemically equivalent amounts of acid and base have reacted is called the equivalence point.
• The point at which a chemical indicator changes color is called the end point.
2color 1color
OH In OH HIn (aq)3(aq))l(2(aq)
bcolor acolor
OH HIn OH In (aq)(aq))l(2(aq)
Acidic indicator
Basic indicator
Acid-Base Indicators• The equilibrium constant expression for an indicator
would be expressed as:
[HIn]
]][InO[H K
-3
a
[HIn]
][In
]O[H
K -
3
a
pH range when indicator changes its color depends
largely on Ka of the indicator
Acid-Base Indicators
Color change ranges of some acid-base indicators
Indicator
Color in acidic range pH range
Color in basic range
Methyl violet Yellow 0 - 2 Purple
Methyl orange Pink 3.1 – 4.4 Yellow
Litmus Red 4.7 – 8.2 Blue
Phenolphthalein Colorless 8.3 – 10.0 Red
Titration CurvesStrong Acid titrated with Strong Base
Given: 25.00 mL of 0.5 M HClO4, calculate the pH of the resulting solution after adding the following volumes of 0.5 M NaOH:
Volume of 0.5 M NaOH
(mL)
Mmoles NaOH
Mmoles HClO4
remaining
TotalVolume
(mL)[H+]final pH
0.00 0.0 12.5 25.0 0.5000 0.301
5.00 2.5 10.0 30.0 0.3333 0.477
10.00 5.0 7.5 35.0 0.2143 0.669
15.00 7.5 5.0 40.0 0.1250 0.903
20.00 10.0 2.5 45.0 0.0555 1.256
25.00 12.5 0 50.0 1x10-7 7.000
30.00 15.0 0 55.0 2.2x10-13 12.657
Methyl orange
Phenolphthalein
Litmus
Methyl violet
• Strong Acid/ Strong Base Titration Curve
Titration CurvesWeak Acid titrated with Strong Base
Given: 25.00 mL of 0.5 M CH3COOH, calculate the pH of the resulting solution after adding the following volumes of 0.5 M NaOH:
Volume of 0.5 M
NaOH (mL)
Mmoles NaOH
Mmoles CH3COOH remaining
Mmoles CH3 COO- produced
TotalVolume
(mL)pH
0.00 0.0 12.5 0 25.0 0.301
5.00 2.5 10.0 2.5 30.0 4.143
10.00 5.0 7.5 5.0 35.0 4.569
15.00 7.5 5.0 7.5 40.0 4.921
20.00 10.0 2.5 10.0 45.0 5.348
25.00 12.5 0 12.5 50.0 9.071
30.00 15.0 0 12.5 55.0 12.658
Methyl orange
Phenolphthalein
Litmus
Methyl violet
WA vs SB Titration Curve Regions
Initial Region: Use ICE and Ka
pH = ½ (pKa + pCHA)
Buffer Region: HH EquationpH = pKa + log (moles A- /moles
HA)
At half equivalence point:pH = pKa
Equivalence Region: Use ICE and Kb pOH =
½ (pKb + p[moles HA/total volume])
Excess base region: pOH = -log (moles excess base/ total
volume)
Buffer Region: HH EquationpH = pKa + log [moles
titrant/(moles analyte – moles titrant )]
Methyl orange
Phenolphthalein
Litmus
Methyl violet
Titration Curve of Different Acids vs
Strong Base
• A 0.1044-g sample of an unknown monoprotic acid required 22.10 mL of 0.0500 M NaOH to reach the endpoint. (a) What is the molecular weight of the acid? (b) As the acid is titrated, the pH of the solution after the addition of 11.05 mL of the base is 4.89. What is the Ka of the acid?
A biochemist needs 750 mL of an acetic acid-sodium acetate buffer with pH 4.50. Solid sodium acetate, NaC2H3O2, and glacial acetic acid, HC2H3O2, are available. Glacial acetic acid is 99% pure by mass and has a density of 1.05 g/mL. If the buffer is to be 0.20 M in HC2H3O2, how many grams of the salt and how many milliliters of glacial acetic acid must be used?
Titration Curves of Polyprotic Acids vs SB
H2A + H2O ⇄ HA- + H3O+ Ka1
HA- + H2O ⇄ A2- + H3O+ Ka2 pH Curve will show: 2 Equivalence points Buffer region similar to weak monoprotic acid region Amphiprotic region
First Equivalence Point: H2A + NaOH ⇄ Na+ + HA- + H2O
Second Equivalence Point: HA- + NaOH ⇄ Na+ + A2- + H2O
Amphiprotic region starts at the 1st equivalence point region. The region between the 1st equivalence point and 2nd equivalence point is a buffer region composed of HA- and A2-. In this region, the buffer HA- and A2- predominates the amphiprotic species HA-.
Weak H2A vs SB
Initial Region: Use ICEpH = ½ (pKa1+ pCH2A)
Buffer Region: HH EquationpH = pKa1 + log (moles
HA- /moles H2A)
Amphiprotic RegionpH = ½ (pKa1 +
pKa2)
Buffer Region: HH EquationpH = pKa2 + log (moles A2-
/moles HA-)
Equivalence Region: Use ICE and Kb1 pOH = ½ (pKb1 + p[moles H2A/total
volume])
Excess base region: pOH = -log (moles excess base/ total
volume)
Weak H3A vs Strong Base Titration
Suppose you want to do a physiological experiment that requires a pH 6.5 buffer. You find that the organism with which you are working is stable to a certain acid and its sodium salts (H2X: Ka1 = 2x10-2, Ka2 = 5.0x10-7). You have available 1.0 M of this acid and 1.0 M NaOH in the lab. How much of the NaOH should be added to 1.0 L of the acid to make a buffer at pH 6.50?
What is the pH of a solution made by mixing 0.30 mole NaOH, 0.25 mole Na2HPO4 , and 0.20 mole H3PO4 with water and diluting with 1.00 L?
H3PO4 pKa1 = 2.12pKa2 = 7.21pKa3 = 12.38