HL Acids and Bases

A. Theories of Acids and Bases

1. Arrhenius theory of A/B
acids = begin with H (produce H+ in water) HCl, H2SO4
bases = end with OH (produce OH = in water) NaOH, KOH,
Mg(OH)2
2. Bronsted-Lowry theory
acids : proton donor
bases: proton acceptor
+
proton= H (hydrogen ion composed of one proton, zero electrons, zero neutron)
proton, hydrogen ion, hydronium ion, H+ : can be used interchangeably
hydronium ion = H3O+ ( water with a proton attached)
Amphoteric = a substance that can be identified as either an acid or a base (depending
on the reaction)

H2O + H2O > H3O+ + OH- the autoionization of water In this case water is a proton
donor and a proton acceptor and so is considered amphoteric

Examples of conjugate acid/base pairs:

An acid reactant will turn into a conjugate base product .
A base reactant will turn into a conjugate acid product.

H2O + H2SO4 > H3O-+ + HSO4-

Base acid conj acid conj base

H2O + NH3 > NH4+ + OH-

A b CA cb

Strong acids  weak conjugate bases

Strong basesweak conjugate acids
** make sure that you maintain electrical charge (or neutrality)

Ka values represent the equilibrium of acids (acting as proton donors)

HCl > H+ + Cl- Ka = [H+] [Cl-]
When Ka is very large value , equilibrium lies far to the right (mostly products at
equilibrium) . By definition, this means a STRONG acid. The larger the Ka values, the
stronger the acid.
When Ka < 1 then the acid is weak (prefers to remain as a molecule, rather than break into
ions)

3. Lewis theory
acids: electron pair acceptor
bases: electron pair donor ** look for atoms with lone pair electrons…N, O…
Example: NH3 + BF3 ---> H3NBF3
LB LA single product
Nitrogen has LP electrons and so is considered the base while B has room to accept a lone
pair of electrons and so is considered the acid.

lewis acids/bases are important in Organic chemistry (remember amines?? ) and non aqueous
media

Bonds formed between lewis A and lewis B are coordinate covalent (dative) bonds.
Complex compounds (ions) are formed with lewis a/b reactions.
Fe+3 + 6 CN- ---> Fe(CN)6 3- **complex ion (with transition metal)
Lewis acids are the most inclusive acids : all Lewis A are BL and Arrhenius acids too.

B. Properties of acids and bases

Acids: sour taste, turn blue litmus paper red, colorless in phenolphtalein
Reactions: 1. acid + metal  H2 + salt
HCl + Mg  H2 + MgCl2
2. acid + metal carbonate  H2CO3 (  H2O + CO2) + salt
HNO3 + Na2CO3  H2O + CO2 + NaNO3
3. acid + base  salt + water (neutralization)
HCl + NaOH  NaCl + HOH
4. acid + hydrogen carbonate compound  salt + H2O + CO2
HNO3 + NaHCO3  H2O + CO2 + NaNO3
5. acid + metal oxide  salt + water ( remember periodicity??)
2 HCl + CuO  CuCl2 + H2O

Bases: alkali = base dissolved in water

Bitter taste, turn red litmus paper blue, pink in phenolphtalein
Bases include metal hydroxides as well as ammonia (NH3) and the BL bases like
HCO3=

C. Strong and Weak acids and bases

Acid and base strength is a measure of the ionization/ dissociation of the compounds.
Strong acids ionize completely (very large Ka values)
Strong bases dissociate completely (very large Kb values)
Dissociation= ionic compound that breaks into ions
Ionization = a covalent compound that forms ions in solution

1. Strong acids Ka is very very large (unspecified) : HCl, H2SO4, HNO3

SA ionize completely ( or to near completion in terms of equilibrium)
SA would rather be ions than compounds
2. All other acids are considered weak
WA ionize incompletely, and would rather be in the compound form, rather than ions
3. Strong bases Kb is very very large (unspecified magnitude) : Group 1 hydroxides and
Ba(OH)2
SB will exist as ions rather than as compound.
4. All other bases (including NH3) are weak.
The degree of strength is determined by Kb value (larger Kb = stronger base)
WB exists primarily as compound, rather than ions.
5. The acid ionization constant :
H2SO4  H+ + HSO4- Ka = [H+] [HSO4-] / [ H2SO4] = very very large
CH3COOH  H+ + CH3COO- Ka = [H+] [CH3COO-] / [CH3COOH]
see data booklet for Ka value
all carboxylic acids are weak acids
6. The base dissociation constant:
KOH  K+ + OH+ Kb = [ K+ ] [OH-] / [KOH] (the denominator approaches
zero)
NH3 + H2O  NH4 + + OH- Kb [ NH4+] [OH-] / [NH3]
7. Determination of strength of acid/ base using experimental data
a. pH meter: lower pH more acidic, higher pH more basic
b. electrical conductivity: stronger A/B has more ions in solution and hence has
greater conductivity.

The pH scale
1. water autoionizes
 HOH + HOH <---> OH- + H3O+
Kc = [OH-][H3O+]= Kw
since K is temp dependent at 25°C Kw = 1.0 x 10-14
Kw = [OH-][H+] = 10-14
so at equilibrium the [OH-] = [H+] in pure water
(pure water has very few ions and is a poor conductor of electricity)
2. in any aqueous solution the Kw expression is valid and may be used, so when [H+]
is very high , [OH-] must be very low
3. when [OH-] =[H+] then solution is Neutral (neither acid nor base)
4. since concentrations can have very small or large numbers,
a logarithmic scale is used to show [H+] and [OH-]
5. the log scale = pH where pH = -log[H+]
6. when [H+] = [OH-] then [H+] = 1 x 10-7 or pH = 7
when pH is lower than 7 = acidic [H+] > [OH-]
when pH is higher than 7 = basic [OH-]>[H+]
** for significant figures - the number of sf in original = # decimal
places in the pH
-6
so 1.0 x 10 , pH = 6.00
2.3 x 10 -8, pH= 7.64
7. pH change of 1 = concentration change of 10 x
8. pH = 10, pH = 11 find [H+]
1x 10 -10 1x 10 -11
9. 14 = pH + pOH or pKw = pH + pOH
when pOH is < 7 basic and > 7 acidic where pOH= -log [OH-]
10. measuring pH
a. pH meter
b. liquid indicator
c. pH paper (paper impregnated with several indicators)
- the usual problems with color interpretation occur with these
11. Small ∆ in pH can have significant changes in environment
: acid rain and its implication for buildings, water, soil, plant

Calculations with acids and bases

A. Kw = [H+] [OH-] = 1.0 x 10-14 ∆H = + 57 kJmol-1 at 298 K.
Equilibrium is temperature dependent so as temp increases the forward rxn is favored
(endothermic reaction uses the heat) and so Kw value increases with increasing temp (more
ions are in solution at higher temperatures ) So, [H+] AND [OH-] both increase at increasing
temperatures so the pH decreases with increasing temp (more H+ ions)
1. When pH or [H+] is known, Kw expression can be used to find [OH-] or pOH
B. Writing Ka expressions as equilibrium reactions
HA > H+ + A- Ka = [H+] [A- ] / [HA]
With a strong acid, [HA] approaches zero and Ka is very very large. Weak
acids have more manageable Ka magnitudes.
C. Calculations with weak acids (using Ka)
1. calc Ka from pH
given: A 0.10M soln of HCHO2(formic acid) and pH is measured at 25°C to be 2.38.
What is Ka? What is % ionization?
a. write equation and work from an equilibrium context --write the table!!
HCOOH <==> H+ + COOH- Ka = [H+][COO-]/ [HCOOH]
I .1M 0 0
∆ -x +x +x
EQ .1 -x x x
Ka = x x/ .1 - x assume that x is <<<<<< .1so Ka = x2/.1
pH = 2.38 = -log[H+] so [H+] = - inverse log 2.38 = 4.17 x 10 -3
Ka = (4.17 x 10 -3 )2 / .1 = 1.8 x 10 -4M

then % ionization = [ionized] / [non-ionized] x 100% = 4.17 x 10-3/ (.1 - 4.17 x 10-3)x 100%
= 4.2% ionization

2. using Ka to calculate pH
What is the pH of a .30 M acetic acid solution? Ka values are in data booklet
using the same equation as before

CH3COOH <===> H + + CH3COO- Ka = [H+][CH3OO-] / [HCOOOH]= 1.8 x 10 -5

initial .3 0 0
∆ -x +x +x
EQ .3 -x x x

so 1.8 x 10 -5 = x2 / .3 - x assume that x << .3

1.8 x 10-5 = x2/ .3
so x = 2.3 x 10-3 = [H+]
-log[H+]= pH = -log 2.3x 10 -3 = 2.64

C.Weak bases- properties and calculations

1. Kb = base dissociation constant = eq constant for dissociation of base into conj acid and
OH-
2. NH3 + HOH <---> NH4+ + OH- Kb = [NH4+][OH-] / [NH3]
3. strong bases will have large Kb while weak bases have small Kb
4. calculation * calc [OH-] ,pOH and pH of a 0.15 M NH3 solution, Kb = 1.8 x 10-5
NH3 + HOH <===> NH4 + + OH- Kb = [NH4+][OH-] / [NH3]
initial .15 0 0
∆ -x +x +x
EQ .15 -x x x

Kb = x2/ .15 = 1.8 x 10 -5 (assume x<<<.15) so x = 1.6 x 10 - 3 M

pOH = - log 1.6 x 10 -3
(pOH= 2.80 and pH = 11.2)
5. relationship between Ka and Kb
a. Ka x Kb = Kw at a given temperature (when Ka increases (stronger acid)
Kb decreases (weaker CB))
to illustrate NH4+ <===> H+ + NH3 Ka = [H+][NH3] / [NH4+]
NH3 + HOH <===> NH4+ + OH- Kb = [NH4+][OH-]/ [NH3]
then Ka x Kb = [H+] [OH-] = Kw
b. pKa + pKb = pKw (adding logarithms)

Salt Hydrolysis
A. salt solutions (ionic compounds dissolved in water)
1. may form solutions that are either acidic or basic depending on type of ions
formed
2. hydrolysis = reaction of ions with water to form either H+ or OH-
3. an anion, X-, can be considered the conjugate base of an acid HX
if HX is a strong acid then the X- will remain as an ion
if HX is a weak acid then X- will combine with H+ to form HX (and release OH-)
X- + HOH <---> HX + OH-
when equilbrium is to the right then the salt forms a more basic solution
when eq is to the left the salt forms a neutral solution
4. when a cation reacts with HOH, it can form H+ ions
NH4+ + HOH <-----> NH3 + H3O+
when eq is to the right then a more acidic solution is formed
 5.salts of SA and SB will not effect pH
6. salts of WA and SB will increase pH
7. salts of WB and SA will decrease pH
8. if several salts are combined, the conjugate of the acid / base with the largest
ionization constant will effect the solution most.
9. metal ions will cause a decrease in pH ( excess H+)
due to the LEWIS concept of acid and base
metal ions have + charge and can accept lone pairs (metal = lewis acid)
metal + charge attracts the unshared electrons from water (hydration)
metal ion =LA water = LB
this flow of electron density away from the water, causes the HO bond to become
more polarized, and as a result water molecules bonded to metal ions are more
acidic than those water molecules in the pure solvent.
Fe(H2O)6 3+ <====> Fe(H2O)5(OH-)2+ + H+
this hydrated ion acts as a source of protons
10. acid dissociation constants increase in magnitude with increasing charge and
decreasing radius of ion
(Cu 2+ is larger and has lesser charge so is less acidic than Fe3+, smaller and
greater charge)
*****note that metals of SA and SB do not exhibit B or A properties ( they are neutral)

11. examples
a. will Na2HPO4 act as acid or base?

Na2HPO4 + HOH <-----> NaH2PO4 + OH- pH will increase

HPO4-2 +HOH <----> PO43- + H3O+ pH will decrease
since successive removal of H+ from a polyprotic acid decreases the ionization constant,
the first reaction is more likely
b. list the following in order of increasing acidity ( decreasing pH)
0.1 M of the following: Ba(C2H3O2), NH4Cl, KNO3

Ba 2+ - conj A of SB - no effect C2H3O2 - conj b of WA therefore pH increase

NH4Cl NH4+ is conj A of WB therefore pH decrease Cl- is conj B of SA no effect
K+ is conj A of SB, NO3- is conj B of SA therefore neutral solution
answer: C2H3O2Ba < KNO3< NH4Cl

12. The simplification : determine the acid and base from which the salt is formed.
The following combinations give the following types of salts:
SA + SB  neutral salt (numbers of H+ and OH- ions cancel each other)
SA + WB  acidic salt (more H+ than OH-)
WA + SB  basic (alkaline) salt (fewer H+ than OH- )

13. The explanation of the acidity of the salt must include a discussion of the free ions and
their origin.

Buffer Solutions
1. Buffer definition- a solution that can resist drastic changes in pH upon addition of small
amounts of SA or SB.
a. buffers contain both an acidic species to neutralize OH-, and a basic species to
neutralize H+. These parts together make up a buffer. Composition is a weak a/
b conjugate pair (like acetic a and acetate ion). Prepared by combining WA or
WB with the salt of the conjB or conj A. ** or with a small amount of SB /SA
b. correct choice of buffer and [ ] will allow a buffer system for about any pH
c. the equilibrium involved is
 HA <----> H+ + A- Ka = small (weak A)
d. qualitative explanations
HF <-------> H+ + F-
when H + is added to system EQ shift to left forming more acid and removing H+
from the solution
when OH- is added HF + OH- ---> F- + HOH removes OH- and maintains
stable pH.
as long as the ratio of HF to F remains close, the system will act as a buffer.
e. buffer capacity- the amount of A or B the buffer is able to neutralize before the
pH changes
- dependent on the amounts of acid and conj base in the system
f. pH of buffer depends on the ka of the weak acid/base from which it is made
g. the common ion effect calculations may be used for buffer systems
Common Ion Effect
1. adding an ion to a system at eq will change that eq by reducing the amount of
added ion
2. example CH3COOH <====> CH3COO- + H+
when CH3COONa is added, CH3COO - ions and Na + ions are added
the CH3COO - ions shift the eq to the left and decreases the EQ [H+]
3. quantitative ex. ? pH of a solution made by adding 0.30 mole acetic A and
0.30 mole of sodium acetate to enough water to make 1 L solution?
.3 mole CH3COONa ===> .3 mol Na, and .3 mol CH3COO-
.3 mole CH3COOH <---> eq find [ ] using the Ka expression

CH3COOH <-----> CH3COO- + H+

initial .3 M .3 M 0
∆ -x +x +x
EQ .3 - x .3 + x x

Ka = [CH3COO-] [H+] / [CH3COOH] = 1.8 x 10-5 (look up value)

Ka = .3 x / .3 assume that x <<<< .3
1.8x 10 -5 = x = [H+] so pH = - log 1.8 x 10 -5 = 4.74

4. another problem
Calculate the[ F-] and pH of a solution that is .20 M in HF and 0.10 M in HCl

HCl ========> H+ + Cl-

HF <---------> H+ + F- common ion is H

HF H+ F-
initial .20 .1 M 0
∆ -x +x +x
EQ .2 -x .1 + x x

Ka = [H+][F-] / [HF] = 6.8 x 10-4 = .1x/.2 *****assume that X<<.1

x = [F-] = 1.4 x 10 -3

pH = -log [H+] = -log (.1 + 1.4 x 10-3) = 1.00 (all the H+ comes from HCl)
5. yet another calc the formate ion concentration and pH of a solution that is .05 M
in formic acid (HCOOH, Ka = 1.8 x 10-4) and 0.10 M in HNO3

answer : [COO-] = 9.0 x 10-5, pH = 1.00

2. buffer equation = Henderson - Hasselbach equation

pH = pKa + log[base]/[acid] (answers can be found using stepwise calc too.)
example: What is the pH of a buffer that is 0.12 M in lactic acid and 0.10 M in sodium
lactate. Ka = 1.4 x 10-4

HA <======> H+ + A-
I .12 0 .1
∆ -x +x +x
EQ .12 - x x .1 +x
Ka = .1x / .12 = 1.4 x 10 -4 ****assume x <<< .1
+ -4 +
X = [H ] = 1.7 x 10 then -log [H ] = 3.77 or use H-H equation to get the same answer

3.Calculations of pH after addition of A or B to buffer

1. stoichiometry calc - determine effect of neutralization on [HX] [X]
2. equlibrium calc - as always using Ka
3. Example
a buffer made by adding .300 mol of acetic A to .300 mol sodium acetate to
enough water to make a 1 liter solution . the pH of the buffer is 4.74.
calculate the pH of this solution after .02 mol of NaOH is added?
pH when .020 mol of NaOH were added to 1.00 L of pure water?
CH3COOH + OH- <-----> HOH + CH3COO- this is the A+ B Salt + water
before rxn : .3 mol .02 mol .300 mol

(in a buffer we assume that all of the added base is consumed)

after rxn: .280 mol 0 .320 mol

now use eq expression

CH3COOH <=====> CH3COOO- + H+

Initial .28 .32 0
∆ -x +x +x
EQ .28 - x .32 + x x ***assume X<<<< .28 and .32
-5 -5
Ka = .32x /.28 = 1.8 x 10 so x= 1.5x10 = pH = 4.80

or use HH eq pH= 4.74 + log .32/.28 = 4.80

for water ... HOH <----> H+ + OH-

x .2
Kw = 1x 10 -14= .2x
x = 5 x 10 -14 pH = 13.30 ** note that the pH changes dramatically when a buffer is not
used.

Acid-base Titrations
1. Important parts of titrations
a. purpose - to find the [ ] of an acid or base (in neutralization reactions )
b. accurate measurement by pH meter or burette use
c. Indicators are used to show (visually) the EQUIVALENCE POINT of the
reaction
d. EQUIVALENCE point = stoichiometric amount of acid = amount of base
e. Titration Curve shows graphically how the titration effects pH of the solution
f. different combinations of A/ B give typical types of titration curves.
2. SA/ SB titrations
a. titration curve = starts at low pH straight (vertical) line at eq pt and ends at high
pH
b. assume that we will titrate a SB (.1 M NaOH) with a SA (.1 M HCl) 50 ml
c. note that acid dissociates completely as does base
 d. the rxn NaOH + HCl ====> NaCl + HOH
e. we will calc pH at various volumes and create a titration curve
f. initial pH when .1 M HCl [H+] initial is all from HCl so [H+] = .1 so pH = 1
g. equivalence point ( when moles H+ = mole OH-)
so HCl .1 mol/ l L x .05 L = .005moles EQ pt = when .005 moles NaOH is
added
so NaOH .005 moles x 1L/ .1 mol = .05 L NaOH added
at this point all H+ and OH- from A and B are consumed to form product and pH = 7
( since H+ and OH- come only from water)
h. below eq. point for example 49 ml NaOH added
from above .005 moles H+ available and .049L x .1 mol NaOH/ 1 L = .0049 mole OH-
before rxn .005 .0049
H+ OH- ====> HOH
after rxn 005 - .0049= .001mol 0
[H ]= .001 mol/ (.050 l + .049 l ) = 1.0 x 10 -2 pH = 2.00
+

i. past eq point
when 51 ml of NaOH added
all acid is consumed .005 mole acid and .0051 mole OH- so excess OH-
= .0001 mol OH- / .101 L = .00099 M = [ OH-] , pOH = 3.00 so pH = 11.00

j. choosing indicators
1.ideally indicator should change at eq pt, but since the pH changes so drastically
at eq pt , an indicator which changes color anywhere within the vertical part of the
titration curve will work.
2. how indicators work
indicators HIn <---> H+ + In-
color dif color
addition of H+ will force EQ <---- to “color”
addition of OH- will force EQ ---> to “ dif color”
The END POINT is when the indicator changes color ( this does not necessarily
have to be at the eq point)
Phenolphthalein is a common indicator for SA/SB titrations
k. IF a base is titrated with a strong acid, then the curve would be opposite (starts
high and ends low)

3. WA/ SB titrations
a. titration curve - pH begins at a higher value, ends at high value, vertical area is
shorter and less straightly vertical
b. outline of calc procedure
1. stochiometric cal of neutralization, then eq calculation to find pH
. 50 ml of .1 M acetic acid with.1 M NaOH.
a. calc initial ( no base is added yet)
CH3COOH <====> CH3COO- + H+
Ka = 1.8 x 10 -5 = x2
x =[H+] =4.24 x 10-3 pH = 2.37

b. calc at equiv point

.05 ml acid .1 mole/1L acid = .005 mole acetic acid and .005 mole of NaOH
NaOH + CH3COOH >HOH + CH3COONa
water is neutral (no effect on pH) but CH3COONa will ionize and affect pH
CH3COONa ------> CH3COO- + Na+
sodium ion has no effect on pH but the acetate ion will react with H+ to reform
acetic acid so the pH of the equivalence point will be above 7
How to find the pH at eq. pt.
solution of .005 molesCH3COO-
 CH3COO- + HOH ====> CH3COOH + OH-
I .005/.1liter 0 0
∆ -x +x +x
EQ .05M - x x x
Kb = Kw/ Ka = 1x10-14/ 1.8 x 10-5= 5.6x 10-10= [CH3COOH][OH-]/ [CH3COO-]
5.6 x 10-10 = x2/.05 = 5.29x10-6=[OH-], pOH=5.28, pH=8.72

c. calc before eq pt
when 50 ml acid + 45 ml base
before rxn .005 mole .0045mol
CH3COOH + NaOH =-=> CH3COONa + HOH
after rxn .0005mole 0 .0045mol total vol= .095L

Ka=[H+][CH3COO-]/[CH3COOH] =
1.8 x 10-5 = [H+] (.0045mol/.095L/ (.0005mol/.095L)
[H+] = 2.0 x 10-6 pH = 5.70

d. calc after eq pt
CH3COOH + NaOH after eq pt excess OH- so just solve for pOH then pH
for example
.1 M CH3COOH 50 ml and .1 M NaOH and 55ml NaOH
before rxn .005mole .0055 mol
CH3COOH + NaOH =====> CH3COONa + HOH
after rxn 0 .0005 mol .0005 mol (the contribution of this is minor
compared to the excess OH-)

in effect what is pH of .0005mol NaOH in 105ml

.0005/.105= .0048 M assume that [OH-] = .0048M
pOH =2.32 pH=11.68

SA/WB would show similar methods of solving for pH except pH is lower to begin with and
end with pH at eq point will be below 7

c. In general:
1. Initial conditions -- only acid ions
2. eq pt- formation of salt - find pH using that info
3. before eq pt - find [ion] [acid]
4. after eq pt [OH]
d. Sketch the general shapes of pH v. volume for titration with SA, SB, WA,WB and explain
intercept with pH axis, equivalence point, buffer region, points where pka =pH or pKb =
pOH (half equivalence points)