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AqueousEquilibria:
AcidandBase
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AcidBaseConcepts:
Arrhenius theor of acids and bases.
Acids substances that dissociate in water to producehydrogen ions.
HA (aq) H+ (aq) + A (aq)
Bases substances that dissociate in water to produceh droxide ions.
MOH (aq) M+ (aq) + O H (aq)
Limitations to theory.
restricted to aqueous solutions doesn't account for the basicity of substances that don't
contain OH groups
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AcidBaseConcepts:
Acid any substance that can transfer a proton to.
Base any substance that can accept a protonroton acce tor .
Acidbase reaction protontransfer reactions
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AcidBaseConcepts:
whose formulas differ only by one proton.
.
A is the conjugate base of HA
.
BH+ is the conjugate acid of B
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AcidBaseConcepts:
.
acid transfers a proton to the solvent, which acts.
HA (aq) + H2O (l) H3O+ (aq) + A (aq)
.
Base accepts a proton from the solvent, which
. NH3 (aq) + H2O (l) OH
(aq) + NH4+ (aq)
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AcidBaseConcepts:
lone pairs of electrons.
the proton.
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BronstedLowry
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Bronsted
Lowry
acid
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Bronsted
Lowry
base
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AcidBaseConcepts:
Write the proton transfer equilibria for the
and identify the conjugate acidbase pairs in
each one: C6H5NH3
+ (anilinium ion),
H2PO4 (acid reaction),
NH2NH2 (hydrazine, a base), and
PO43.
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AcidBaseConcepts:
+ +
Conjugate acidbase pairs:
6 5 3 6 5 2 2 3(acid)
+2 4 2 4 3
Conjugate acidbase pairs:
2 4
ac 4
ase ; 2 ase 3(acid)
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AcidBaseConcepts:
+
Conjugate acidbase pairs: 2 2 2 3 2
(base)
4 2 4
Conjugate acidbase pairs:
4
ase 4
ac ; 2 ac
ase
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AcidStrengthand
,
bases, H2O and A, are competing for protons.
proton transfer from the stronger acid to the
stron er base.
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AcidStrengthand
aqueous solution..
H2O is a stronger base than A
solution.
v g ug . A is a stronger base than H2O
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Conjugate
acid
basepairs
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AcidStrengthand
Determine the direction of reactions involving:
acet c ac , acetate on, y rosu ur c ac , an
acetic acid, acetate ion, hydrogen sulfate, and4 .
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AcidStrengthand
HSO4(aq)+CH3CO2
(aq)SO42(aq)+ CH3COOH
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Introduction
to
aqueousacids
Introductiontoaqueousacids
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Introductiontoaqueous
bases
IntroductiontoaqueousBases
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HydratedProtons
+ +
an
y ron um ons
,
to the oxygen atom of a solvent water molecule. +
produces higher hydrates through hydrogen bonding with
other water molecules genera ormu a 2 n
+ +3
proton hydrated by an unspecified number of water
molecules.
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Dissociationof
a er
Dissociation of water one water molecule
H2O (l) + H2O (l) H3O+ (aq) + O H (aq).
Ion roduct constant for water Kw.Kw = [H3O
+] [OH ]
Forward and reverse reactions are rapid.
Position of the equilibrium lies far to the left. In an aqueous solution, [H3O
+][OH] = 1.0 x 1014
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Dissociationof
Relative values of H O+ and OH concentrations can be
a er
used to determine if an aqueous solution is neutral,acidic or basic.14
[H3O+
] .
[OH- ]
1.0 1014
[H3O+] = [OH], neutral solution and [H3O
+] = 1.0 x 107 M.
[OH-]
[H3O+ ]
H3+
> H
, ac so ut on an H3+
> 1. x 1
M. [H3O
+] < [OH], basic solution and [H3O+] < 1.0 x 107M.
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Dissociationofwater
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Dissociationof
a er
Calculate the molarity of OH in a solution
3 . .
solution acidic, basic or neutral?
Is a so ut on w t an OH concentrat on o 8.5
105 M acidic, basic or neutral?
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Dissociationof
+
a er
,
calculate the other from the relationship+
3 .
OH-
1 1014
2.9 1014
Since [H3O+] > 1.0 107 this solution is acidic.
.
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Dissociationof
a er
14
H3O+
.
8.5 10 5 1.2 10
n s case, 3 < . ;
therefore, the solution is basic.
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the hydronium ion concentration.+ 3 .
[H3O+] = antilog(pH) = 10pH.
the right of the decimal point.
number related to the integral power of 10 in the
exponential expression for [H3O+]
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+
.
Acidic solutions, pH < 7.
, .
Neutral solutions, pH = 7.
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change color in a specific pH range..
Have different colors in their acid (HIn) and .
Change color over a range of 2 pH units.
pH unit.
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.
An electronic instrument that measures a pH.
Determines pH values more accurately than acid
base indicators.
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Acidbaseindicators
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Naturalindicators
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Calculate the pH of a 1.25 x 103 M HNO3 solution.
HNO3 is a strong acid which completely dissociates
in water. Therefore, [H3O
+] = initial concentration of theundissociated acid.
[H3O+
] = 1.25 x 103
M pH = log [H3O
+] = log (1.25 x 103) = 2.903
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ThepHofstrongacids
an
strong
ases
solution (HClO4, HCl, HNO3).+
3 .
[undissociated HA] = 0.
, = 3
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ThepHofstrongacids
an
strong
ases
.
Alkali metal hydroxides, MOH.
exist in aqueous solution as alkalimetal cations and
hydroxide anions calculate pH from [OH]
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ThepHofstrongacids
an
strong
ases
.
Alkalineearth metal hydroxides, M(OH)2 (M = Mg,, , .
less soluble than alkali hydroxides, therefore lower [OH]
most important strong base lime, CaO produces Ca(OH)2 when mixed with water
used in steel making, water purification, and chemical
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Equilibria inSolutions
Weak acids artiall dissociated can write an acid
o
ea
c s
dissociation equilibrium equation.
HA (aq) + H2O (l) H3O+ (aq) + A (aq)
Pos t on o ac ssoc at on equ r um c aracter zeby the aciddissociation constant, Ka.
-
The lar er the value ofKa the stron er the acid.
Ka 3
[HA]
Ka values can be determined from pH measurements.
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Aciddissociationconstant
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Equilibria inSolutions
o
ea
c s
The pH of a 0.200 M solution of nicotinic acid6 4 2 . .
Determine the value ofKa for this acid.
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Equilibria inSolutions
o
ea
c s
To determine Ka first write the balanced
the equilibrium equation that defines Ka.
HC6H4NO2 aq +H2O H3O+ aq +C6H4NO2 aq
+ -
Ka 3 6 4 2
[HC6H4NO2 ]
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Equilibria inSolutions
o
ea
c s
concentrations of the species in the.
concentration of H3O+ from the pH.
3 . .
x 103 M.
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Equilibria inSolutions
o
ea
c s
produces one H3O+ and C6H4NO2
ion; the H3O+
6 4 2 .
[H3O+] = [C6H4NO2
] = 1.66 x 103 M
T e HC6H4NO2 concentrat on at equ r umis equal to the initial concentration minus the
amount o 6 4 2 t at ssoc ates.
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U S O SO
Equilibria inSolutions
o
ea
c s
is equal to the initial concentration minus the6 4 2 .
[HC6H4NO2] = 0.200 (1.66 x 103) = 0.198 M
[H3O+ ][C6H4NO2
- ] 1.66 103 1.66 10 3 5
a
[HC6H4NO] 0.198
.
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CalculatingEquilibriumConcentrationsinWeak
AcidSolutions
solution of a weakacid can be calculated from.
To solve acidbase equilibrium problems, think
.
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CalculatingEquilibriumConcentrationsinWeak
AcidSolutions
Calculate the concentration of all species
3 , 4 7 2 , 4 7 2,
the pH in 0.250 M butyric acid (HC4H7O2).
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CalculatingEquilibriumConcentrationsinWeak
The s ecies resent initiall are HC H O acid
AcidSolutions
and H2O (acid or base)
The possible protontransfer reactions areHC4H7O2(aq) + H2O (l) H3O
+ (aq) + C4H7O2 (aq)
Ka = 1.5 x 105
H2O (l) + H2O (l) H3O+ (aq) + OH (aq)
Kw = 1.0 x 1014
Since Ka >> Kw, the principal reaction isdissociation of HC4H7O2.
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CalculatingEquilibriumConcentrationsinWeak
HC H O =0.250x
AcidSolutions
[H3O+
]
=
x [C4H7O2 ]=x
Ka 1.5 10
5
[H3O+][C4H7O2
- ]
x x
Assume that x is negligible compared with the
4 7 2 .
. x 0.250.
Usin this value in the denominator solve for x.
x 1.9 103
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CalculatingEquilibriumConcentrationsinWeak
AcidSolutions
Ka 1.5 105
[H3O+][C4H7O2- ]
HC H O x x
0.250 x
x 1.9 103
Thebigequilibriumconcentrationsare[HC4H7O2]=0.250 0.0019=
0.248M;[H3O+]=[C4H7O2
]=1.9x103 M
K 1.0 10 14[OH
-] w
[H3O+]
1.9 103 5.3 10
3 . .
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P t Di i ti i
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PercentDissociationin
ea
c
o u ons
[HA] dissociatedercen ssoc a on =
[HA] undissociated
Value depends on the acid.Increases with increasing value ofKa.
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P t
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Percent
dissociation
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id di i ti
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aciddissociation
constant
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Pol rotic acids
one dissociable proton..
Each dissociation step has its own Ka.
Stepwise dissociation constants decrease inthe order Ka1 > Ka2 > Ka3.
More difficult to remove a positively chargedproton from a negative ion.
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Pol rotic acids
acids, H2A, HA
, and H2O. 2 .
principal reaction dissociation of H2A
3
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Equilibria in Solutions
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Equilibria inSolutions
o
ea
ases
basedissociation equilibrium equation+
2
Position of basedissociation equilibrium
constant, Kb.BH+ OH-
Kb
[B]
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Equilibria in Solutions
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Equilibria inSolutions
C. Amines or anic com ounds that are weak
o
ea
ases
bases.
Derivatives of ammonia.
One or more hydrogen atoms are replaced by anothergroup.
. can be used for bonding to a proton
To solve for e uilibrium concentrations and
solution pH, use the same procedure for solvingweak acid problems.
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RelationBetweenKa
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For a con u ate acidbase air, can calculate
an
either Ka or Kb from the other.
Sum of an aciddissociation reaction and a base.
Equilibrium constant for the net reaction (dissociation
of water) = the product of the equilibrium constantsfor the individual reactions.
Ka Kb = Kw. ,
conjugate base must decrease as the strength of theacid increases.
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RelationBetweenKa
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EXAMPLE:
an
CalculateKb forlacticacid(HC3H5O3)givenKa =1.4
104.
b.
Kw =Ka Kb;
14
Kb w
Ka
Kb 1.4 10 4
7.14 1011
3 5 3
aq +2
3 5 3
+
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AcidBasePropertiesof
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a ts
base properties of the constituent cations andanions.
In an acidbase reaction, the influence of thestronger partner is dominant.
strong acid + strong base neutral solution
strong acid + weak base acidic solution
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AcidBasePropertiesof
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a ts
.
Derived from a strong base and a strong acid.
to produce H3O+ or OH ions.
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AcidBasePropertiesof
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a ts
.
Derivedfromaweakbaseandastrongacid. .
Cation isaweakacid.
+ 3
small,highlychargedcations arealsoacidic
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AcidBasePropertiesof
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a ts
.
Derived from a strong base and a weak acid. .
Anion is a weak base.
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AcidBasePropertiesof
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a ts
anions.
Derived from a weak acid and a weak base.
Both the cation and the anion can undergoprotontransfer reactions.
pH depends on the relative acid strength of thecation and the base strength of the anion.
Kb (for the anion) > Ka (for the cation); basic solutionKa (for the cation) = Kb (for the anion); neutral solution
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AcidBasePropertiesof
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a ts
Determine whether aqueous solutions of the, .
Write the hydrolysis reaction for those
.NH4Br, K3PO4, CsI, [(CH3)3NH]F.
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AcidBasePropertiesof
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a ts
aqueous solution of a salt, we must determine
1) a strong acid/strong base reaction,
, 3) strong acid/weak base reaction, or
w w .
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AcidBasePropertiesof
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a ts
acid:3 2,
derived from NaOH and HCl and from Ca(OH)2 and
HNO res ectivel . Neither cation nor anion hydrolyzes.
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AcidBasePropertiesof
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a ts
acid:
conjugate base.
2 3 2 2. The anion hydrolyzes to produce OH(aq) ions.
.
The solution has a pH above 7.
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AcidBasePropertiesof
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a ts
acid:
conjugate acid.
4 3 3. The cation hydrolyzes to produce H+(aq) ions.
.
The solution has a pH below 7.
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AcidBasePropertiesof
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a ts
Examples are NH4C2H3O2, NH4CN, and FeCO3. .
The pH of the solution depends on the extent towhich each ion hydrolyzes.
The pH of a solution of NH4CN is greater than 7because CN (Kb = 2.0 10
5) is more basic than
NH4+ Ka = 5. 1
s ac c.
Consequently, CN hydrolyzes to a greater extent than+
4 .
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AcidBasePropertiesof
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a ts
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AcidBasePropertiesof
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a ts
and the strong acid HBr (aq). Acidic (NH4
+ isthe weak conjugate acid of NH ).
NH4+ (aq) + H2O NH3 (aq) + H3O
+ (aq)
K PO : derived from the stron base KOH aand the weak acid HPO42 (aq).
Basic PO 3 is the weak con u ate base of
HPO42
.) PO 3 a + H O HPO 2 a + OH
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AcidBasePropertiesof
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a ts
and the strong acid HI (aq). Neutral.
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Acidbase
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propertiesof
salts
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Acidbase
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propertiesof
salts
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FactorsthatAffectAcid
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trengt
often determined by the strength and polarity .
The weaker the HA bond, the stronger the acid.
,acid.
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Factorsthataffect
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acidstrength
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FactorsthatAffectAcid
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trengt
.
HAbondstrengthdecreasesdownagroupinthe.
increaseinthesizeofAdownagroupproducespoorerorbitaloverlapandaweakerbond
HAbondstrengthisthemostimportantfactorfordeterminingacidstrengthforbinaryacidsof
elementsinthesamecolumn.
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FactorsthatAffectAcid
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trengt
.
HA bond polarity is the most important factor for
elements in the same row.
increaseinHAbondpolarityastheelectronegativity ofAincreases
ingeneral,electronegativities increasefromlefttoright
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Factorsthataffect
id h
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acidstrength
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Factorsthataffect
id h
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acidstrength
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FactorsthatAffectAcid
t t
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=
trengt
, ,
and m are integers).
groups.
can also be bonded to one or more ox en atoms Dissociation of oxoacid involves breaking an OH
bond.
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FactorsthatAffectAcid
t t
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=
trengt
and m are integers).
Stren th of the acid increases as the OH bond isweakened or becomes more polar.
For oxoacids that contain the same number of OH
,increases with increasing electronegativity of Y.
For oxoacids that contain the same atom Y but differentnum ers o oxygen atoms, ac strengt ncreases w t
increasing oxidation number of Y, which increases, inturn, with an increasing number of oxygen atoms.
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Factorsthataffect
id t th
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acidstrength
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Factorsthataffect
acid strength
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acidstrength
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Factorsthataffect
acid strength
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acidstrength
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LewisAcidsandBases
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.
All Lewis bases are BrnstedLowry bases.
.
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LewisAcidsandBases
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.
More general definition than BrnstedLowry.
vacant valence orbitals that can accept a share in
Cationic Lewis acids metal ions.
and oxides of nonmetals.
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Lewisacidbase
theory
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theory
Lewisacidbasetheory
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Lewisacidbase
theory
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theory
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Lewisacidbase
theory
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theory
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