Acids and bases, pH and buffers

Dr. Mamoun Ahram

Lecture 2
ACIDS AND BASES
Acids versus bases
Acid: a substance that produces H+ when dissolved
in water (e.g., HCl, H2SO4)

Base: a substance that produces OH- when dissolved
in water (NaOH, KOH)

What about ammonia (NH3)?
Brnsted-Lowry acids and bases
The Brnsted-Lowry acid: any substance able to give
a hydrogen ion (H+-a proton) to another molecule
Monoprotic acid: HCl, HNO3, CH3COOH
Diprotic acid: H2SO4
Triprotic acid: H3PO3

Brnsted-Lowry base: any substance that accepts a
proton (H+) from an acid
NaOH, NH3, KOH

Acid-base reactions
A proton is transferred from one substance (acid) to
another molecule
Ammonia (NH
3
) + acid (HA) ammonium ion (NH
4
+
) + A-
Ammonia is base
HA is acid
Ammonium ion (NH
4
+
) is conjuagte acid
A
-
is conjugate base


Water: acid or base?
Both
Products: hydronium ion (H
3
O
+
) and hydroxide
Amphoteric substances
Example: water
NH
3 (g)
+ H
2
O
(l)
NH
4
+
(aq)
+ OH

(aq)


HCl
(g)
+ H
2
O
(l)
H
3
O
+
(aq)
+ Cl
-
(aq)

Acid-base reactions
Acid + base salt + H2O
Exceptions:
Carbonic acid (H
2
CO
3
)-Bicarbobate ion (HCO
3
-
)




Ammonia (NH
3
)-
Acid/base
strength
Rule
The stronger the acid, the weaker the conjugate base
HCl
(aq)
H
+
(aq)
+ Cl
-
(aq)
NaOH
(aq)
Na
+
(aq)
+ OH
-
(aq)


HC
2
H
3
O
2 (aq)
H
+
(aq)
+ C
2
H
3
O
2
-
(aq)
NH
3 (aq)
+ H
2
O
(l)
NH
4
+
(aq)
+ OH
-
(aq)



Equilibrium constant
HA <--> H+ + A-




K
a
: >1 vs. <1
Expression
Molarity (M)
Normality (N)
Equivalence (N)
Molarity of solutions
moles = grams / MW

M = moles / volume (L)

grams = M x vol (L) x MW

Exercise
How many grams do you need to make 5M NaCl
solution in 100 ml (MW 58.4)?

grams = 58.4 x 5 moles x 0.1 liter = 29.29 g

Normal solutions

N= n x M (where n is an integer)

n =the number of donated H
+

Remember!
The normality of a solution is NEVER less than the
molarity

Equivalents
The amount of molar mass (g) of hydrogen ions that
an acid will donate
or a base will accept


1M HCl = 1M [H+] = 1 equivalent
1M H2SO4 = 2M [H+] = 2 equivalents


Exercise
What is the normality of H
2
SO
3
solution made by
dissolving 6.5 g into 200 mL? (MW = 98)?
Example
One equivalent of Na+ = 23.1 g
One equivalent of Cl- - 35.5 g
One equivalent of Mg+2 = (24.3)/2 = 12.15 g

Howework:
Calculate milligrams of Ca+2 in blood if total
concentration of Ca+2 is 5 mEq/L.

Titration
The concentration of acids and bases can be
determined by titration
Excercise
A 25 ml solution of 0.5 M NaOH is titrated until
neutralized into a 50 ml sample of HCl. What was the
concentration of the HCl?
Step 1 - Determine [OH
-
]
Step 2 - Determine the number of moles of OH
-
Step 3 - Determine the number of moles of H
+

Step 4 - Determine concentration of HCl

A 25 ml solution of 0.5 M NaOH is titrated
until neutralized into a 50 ml sample of HCl
Moles of base = Molarity x Volume
Moles base = moles of acid
Molarity of acid= moles/volume
Another method



M
acid
V
acid
= M
base
V
base


Note
What if one mole of acid produces two moles of H+

M
acid
V
acid
= 2M
base
V
base


Homework
If 19.1 mL of 0.118 M HCl is required to neutralize
25.00 mL of a sodium hydroxide solution, what is the
molarity of the sodium hydroxide?

If 12.0 mL of 1.34 M NaOH is required to neutralize
25.00 mL of a sulfuric acid, H2SO4, solution, what is
the molarity of the sulfuric acid?
Equivalence point
Ionization of water




H3O+ = H+
Equilibrium constant





Keq = 1.8 x 10
-16
M
Kw






Kw is called the ion product for water
PH
What is pH?
Acid dissociation constant
Strong acid
Strong bases
Weak acid
Weak bases
pKa
What is pKa?
HENDERSON-HASSELBALCH
EQUATION
The equation
pKa is the pH where 50% of acid is dissociated into
conjugate base
BUFFERS
Maintenance of equilibrium
What is buffer?
Titration
Midpoint
Buffering capacity
Conjugate bases
Acid Conjugate base
CH
3
COOH CH
3
COONa (NaCH
3
COO)
H
3
PO
4
NaH
2
PO
4

H
2
PO
4
- (or NaH
2
PO
4
) Na
2
HPO
4

H
2
CO
3
NaHCO
3

How do we choose a buffer?
Problems and solutions
A solution of 0.1 M acetic acid and 0.2 M acetate ion. The pKa of
acetic acid is 4.8. Hence, the pH of the solution is given by



Similarly, the pKa of an acid can be calculated
Exercise
What is the pH of a buffer containing 0.1M HF and
0.1M NaF? (Ka = 3.5 x 10-4)
Homework
What is the pH of a solution containing 0.1M HF and
0.1M NaF, when 0.02M NaOH is added to the
solution?
At the end point of the buffering capacity of a buffer,
it is the moles of H
+
and OH
-
that are equal
Exercise
What is the concentration of 5 ml of acetic acid
knowing that 44.5 ml of 0.1 N of NaOH are needed to
reach the end of the titration of acetic acid? Also,
calculate the normality of acetic acid.
Polyprotic weak acids
Example:
Hence
Excercise
What is the pH of a lactate buffer that contain 75%
lactic acid and 25% lactate? (pKa = 3.86)

What is the pKa of a dihydrogen phosphae buffer
when pH of 7.2 is obtained when 100 ml of 0.1 M
NaH2PO3 is mixed with 100 ml of 0.1 M Na2HPO3?
Buffers in human body
Carbonic acid-bicarbonate system (blood)
Dihydrogen phosphate-monohydrogen phosphate
system (intracellular)
Proteins


Blood buffering
CO2 + H20 H2CO3 H+ + HCO3-
Blood (instantaneously)
Lungs
(within
minutes)
Excretion via
kidneys (hours
to days)
Roles of lungs and kidneys
Maintaining blood is balanced by the kidneys and the
lungs
Kidneys control blood HCO3 concentration ([HCO3])
Lungs control the blood CO2 concentration (PCO2)
Calculations
Acidosis and alkalosis
Can be either metabolic or respiratory
Acidosis:
Metabolic: production of ketone bodies (starvation)
Respiratory: pulmonary (asthma; emphysema)

Alkalosis:
Metabolic: administration of salts or acids
Respiratory: hyperventilation (anxiety)
62
Acid-Base Imbalances
pH< 7.35 acidosis

pH > 7.45 alkalosis
Respiratory Acidosis
H
+
+ HCO
3
-
H
2
CO
3
CO
2
+ H
2
O
Respiratory Alkalosis
H
+
+ HCO
3
-
H
2
CO
3
CO
2
+ H
2
O
Metabolic Acidosis
H
+
+ HCO
3
-
H
2
CO
3
CO
2
+ H
2
O
Metabolic Alkalosis
H
+
+ HCO
3
-
H
2
CO
3
CO
2
+ H
2
O