15 acids and bases contents 15-1 the bronsted-lowry definitions 15-2 the ion product of water, kw...
TRANSCRIPT
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15 Acids and Bases Contents
15-1 The Bronsted-Lowry Definitions15-2 The Ion Product of Water, Kw15-3 The pH and Other “p” Scales15-4 Concentrations of Hydrogen Ions in Aqueous Solutions of Acids 15-7 The Common Ion Effect15-8 Buffer Solutions15-9 How Indicators Work
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Acids and Bases Arrhenius Definitions - Acids produce hydrogen ions in
aqueous solution, and bases produce hydroxide ions in aqueous
solution.
Brønsted-Lowry Definitions - An acid is a proton (H+) donor,
and a base is a proton acceptor.
Lewis Acid-Base Definitions - An acid as an electron pair
acceptor and a base as an electron donor.
A rrh en iu s B ron s ted /L ow ery L ew is
A c id -B ase C on cep ts
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strong acid formula
hydrochloric HCl hydrobromic HBr hydroiodic HI Nitric HNO3
chloric HClO3
perchloric HClO4
sulfuric H2SO4
Sulfuric acid is the only strong acid that is diprotic, meaning it has two protons to donate.
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Acid H+ donor
Base H+ acceptor
15-1 The Bronsted-Lowry Definitions
Terms to know: proton - H+ ion
hydronium ion - H3O+; results from water reacting with
H+
H2O + H+ --> H3O+
conjugate base - whatever is left from an acid after a
proton has been donated
conjugate acid - whatever has been formed when a
proton has been accepted by a base
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Acids are hydrogen ion (H+) donorsBases are hydrogen ion (H+) acceptors
HCl + H2O H3O+ + Cl-
donor, acid acceptor, base
+ +
HCl/Cl- ; H3O+ / H2O :Conjugate Acid-Base Pair
An acid-base reaction consists of the transfer of a proton for an acid to a base.
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In acidic solutions, the protons (H+) that are
released into solution will not remain alone due to
their large positive charge density and small size.
They are attracted to the negatively charged
electrons on the oxygen atoms in water, and form
hydronium ions.
H+(aq) + H2O(l) = H3O+
(l)[H+] = [H3O+]
OH H
.. ..
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H atom and H+ ion atomic structure? Use symbols H+ and H3O+ to represent the same thing
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Conjugate Acid-Base Pair
• Conjugate acid-base pair consists of two substances
related to each other by the donating and accepting of
a single proton.
• Acids and bases that are related by loss or gain of H+.
• NH3+HCl NH4++ Cl-
• NH4+/NH3, HCl/ Cl-
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A species like water that can react either as an acid or as a base is said to be amphoteric.
HF(aq) + H2O(l) H3O+(aq) + F-(aq)
Acid 1 Base 2 Acid 2 Base 1
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
Base 1 Acid 2 Acid 1 Base 2
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Summary
1. Acids and Bases can be molecules or ions
2. Not just defined in aqueous solutions
3. Conjugate pairs differ by H+
4. Some substances are both, AMPHOTERIC
depending on the reaction.
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• Autoionization: A reaction in which a substance reacts with itself
to form ions.
• Water is the common amphoteric substance.
• HF(aq) + H2O(l) H3O+(aq) + F-(aq) H2O as base.
• NH3(aq) + H2O(l) NH4++ OH- (aq) H2O as acid.
• Kw=[H3O+][OH-]=1×10-14 ion-product constant (25 )℃
• pH=-log[H+]
2H2O(l) H3O+(aq)+OH-(aq)
15-2 The Ion Product of Water, Kw
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• Water
– The most common amphoteric substance
• water can act as both an acid and a base
• water can autoionize:
– H2O + H2O <==> H3O+ + OH-
– one water molecule acts as an acid (H+ donor), the other acts
as an acid (an H+ acceptor)
– Kw = [H3O+][OH-] = 1.00 x 10-14 @ 25oC
• dissociation or ion product constant for water
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• Kw
– In any aqueous solution at 25oC, the product of [H+] and
[OH-] will be 1.0 x 10-14
– So if you know the [H+], you can figure out the [OH-] and
vice versa
– If [H+] = [OH-], the solution is neutral
– If [H+] > [OH-], the solution is acidic
– If [H+] < [OH-], the solution is basic
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• pH scale
– Because the [H+] in any solution is generally quite small, it
is easier to use the pH scale to represent a solution’s
acidity.
– pH comes from the Danish…potenz or strength of the H+
ion
– The pH of a solution is usually defined as the negative of
the base 10 logarithm.
– pH = - log[H+]
– pOH = - log [OH-]
15-3 The pH and Other “p” Scales
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Acids and Bases• pH is a log scale
– when the pH changes by one, the [H+] concentration changes by a power of 10.
• A solution with a pH of 3 has 10 times more H+ than a solution with a pH of 4, and 100 times more H+ than a solution with a pH of 5.
– As pH decreases, the [H+] increases.
– Rule for significant figures for logarithms - the number of places after the decimal point is equal to the number of significant figures in the original number
• pH = - log 1.0 x 10-9 M (2 significant figures in 1.0 x 10-9)
• pH = 9.00 ( 2 places after the decimal point for significant figures)
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Methods for Measuring the pH of an Aqueous Solution
(a) pH paper (b) Electrodes of a pH meter
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Strong and Weak Acids
Strong:Strong: 100% dissociation100% dissociation
good Hgood H++ donor donor
equilibrium lies far to right (HNOequilibrium lies far to right (HNO33))
generates weak base (NOgenerates weak base (NO33--))
Weak:Weak: <100% dissociation<100% dissociation
not-as-good Hnot-as-good H++ donor donor
equilibrium lies far to left (CHequilibrium lies far to left (CH33COOH)COOH)
generates strong base (CHgenerates strong base (CH33COOCOO--))
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15-4 Concentrations of Hydrogen Ions in Aqueous Solutions of Acids
Strong acids:
For dense and moderately dilute solutions (1.0×10-6
to 0.01M) of strong acids that have only one ionizable
hydrogen, [H+] = stoichiometric concentration of the
strong acid.
HCl(aq) H+ (aq) + Cl- (aq)
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HA(aq)+H2O(l) H3O+(aq)+A-(aq)
acid base conjugate acid
conjugatebase
3[ ][ ] [ ][ ]
[ ] [ ]
: acid dissociation constant
a
a
H O A H AK
HA HA
K
HA(aq) H+ ( aq ) +A- ( aq)
Weak acids:
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P584 on the textbook: Table 15.3
Ionization Constants of some Common Weak Acids at 25 ℃
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Ka I
ncre
ases
Strength vs. Ka
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Calculating the pH of Weak Acid Solutions
HF H++F-
1.0MBefore 0 0Equilibrium (1-x)M xM xM
24 2 4
2 4 4 2
2
7.2 10 7.2 10 ( 1)1
7.2 10 7.2 10 2.7 10
log(2.7 10 ) 1.57
a
xK x if x
x
x x
pH
C/K<500
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The 5% Rule
• The validity of an approximation should always be checked.
• The 5% rule should be used to evaluate which approximation are reasonable.
%.%.
.For HF,
%%[HA]
x
-
72100001
1072
5100
2
0
The approximation is acceptable.
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The pH of a Mixture of Weak Acids
HNO2 is assumed to be the dominant producer
of H+.
HCN(aq) H+(aq)+CN-(aq) Ka=6.2X10-10
HNO2(aq) H+(aq)+NO2-(aq) Ka=4.0X10-4
H2O(l) H+(aq)+OH-(aq) Kw=1.0X10-14
4 2
2
[ ][ ]4 10
[ ]a
H NOK
HNO
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HNO2(aq) H+(aq)+NO2-(aq)
5 0 0
5-x x x2 2
4 2
2
2 0
4 10 4.5 105 5
Using the 5% rule
4.5 10100% 100% 0.9%
[ ] 5
a
x xK x
x
x
HNO
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2
-
- 2 -10
- -8
[ ] 4.5 10 1.35
To calculate [CN ]
[ ][CN ] (4.5 10 )[CN ]6.2 10
[HCN] 1
[CN ]=1.4 10 ( )
a
H pH
HK
M
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Percent Dissociation
amount dissociationPercent Dissociation= 100%
initial concentration
HC3H5O3 H++C3H5O3-
0.1 0 00.1-x x x
3
3 34
3.7% 100% 3.7 10 ( )0.1
(3.7 10 )(3.7 10 )1.4 10
0.1a
xx M
K
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15.7 The Common Ion Effect
• Common ion effect: The shift in equilibrium position
that occurs because of the addition of an ion already
involved in the equilibrium reaction.
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The common ion effect is the shift in equilibrium caused by the addition of a compound having an ion in common with the dissolved substance.
The presence of a common ion suppresses the ionization of a weak acid or a weak base.
Consider mixture of CH3COONa (strong electrolyte) and CH3COOH (weak acid).
CH3COONa (s) Na+ (aq) + CH3COO- (aq)
CH3COOH (aq) H+ (aq) + CH3COO- (aq)
common ion
16.2
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A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!
A buffer solution has the ability to resist changes in pH upon the addition of small amounts of either acid or base.
16.3
CH3COOH (aq) H+ (aq) + CH3COO- (aq)
Consider an equal molar mixture of CH3COOH and CH3COONa
Adding more acid creates a shift left IF enough acetate ions are present
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15.8 Buffer Solutions
• A Buffer Solution (or buffered solution) is one that
resists a change in pH when either hydroxide ions or
protons are added.
• A buffered solution may contain a weak acid and its salt
or a weak base and its salt. (HF+NaF, NH3+NH4Cl)
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How Do the H+/OH- Ions Work in Buffered Solutions
• The equilibrium concentration of H+ and the pH are
determined by the ratio [HA]/[A-].
NaA(s) Na+(aq)+A-(aq)H2O(l)
HA(aq) H+(aq)+A-(aq)
][
][][
][
]][[
A
HAKH
HA
AHK aa
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The Effect of Added Bases
When OH- are added, HA is converted to A- , causing
the ratio [HA]/[A-] to decrease. If the amount of HA
and A- originally present are very large compared
with the amount OH- added, the change in [HA]/[A-]
ratio is small.
NaA(s) Na+(aq)+A-(aq)H2O(l)
HA(aq) H+(aq)+A-(aq)
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The Effect of Added Acids
When protons are added to a buffered solution, the added
H+ ions react with A- to form the weak acid. If [HA]
and [A-] are large compared with the [H+] added, only
a slight change in the pH occurs.
NaA(s) Na+(aq)+A-(aq)H2O(l)
HA(aq) H+(aq)+A-(aq)
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Unique Properties of Buffer Solution
• The Effect of Dilution
- The pH of a buffer solution remains essentially
independent of dilution.
• The Effect of Added Acids and Bases
- A buffer solution resists pH change after addition of
small amounts of strong acids or bases
• Buffer Capacity
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Which of the following are buffer systems? (a) KF/HF (b) KCl/HCl, (c) Na2CO3/NaHCO3
(a) KF is a weak acid and F- is its conjugate basebuffer solution
(b) HCl is a strong acidnot a buffer solution
(c) CO32- is a weak base and HCO3
- is it conjugate acidbuffer solution
16.3
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What is the pH of a solution containing 0.30 M HCOOH and 0.52 M HCOOK?
HCOOH (aq) H+ (aq) + HCOO- (aq)
Initial (M)
Change (M)
Equilibrium (M)
0.30 0.00
-x +x
0.30 - x
0.52
+x
x 0.52 + x
16.2
Mixture of weak acid and conjugate base!
KKaa for HCOOH = 1.8 x 10 for HCOOH = 1.8 x 10 -4-4
[H+] [HCOO-]Ka = [HCOOH]
x = 1.038 X 10 -4
pH = 3.98
30.0
52.0108.1
)30.0(
)52.0(
][
]][[ 4 x
x
xx
HCOOH
HCOOHKa
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NaF(s) Na+(aq)+F-(aq)H2O(l)
HF(aq) H+(aq)+F-(aq)
1 0 01-x x x
1 0 01 10
4
[ ][ ] (1 ) ( )(1)
[ ] 1 1
7.2 10
a
H F x x xK
HF x
x
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15.9 How Acid-Base Indicators Work
HIn(aq) H+(aq)+In-(aq)
][
][
][][
]][[
HIn
In
H
K
HIn
InHK a
a
Add a few drops of the phenolphthalein indicator to a acidic solution. (pH=1)
10000000
1
][
][
101
101
][ 1
8
HIn
In
H
Ka
The ratio shows that the predominant form of the indicator is HIn, resulting in a red solution.
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As OH- is added to this solution, [H+] decreases and the
equilibrium shift to right, changing HIn to In-. A color
change from red to reddish purple will occur.
For most indicators, about 1/10 of the initial form must be
converted to the other form before a new color is
apparent.
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Indicators