1. Acids and bases, pH and buffers
Dr. Mamoun Ahram
Lecture 2

2. Acids and bases

3. 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)?

4. Brønsted-Lowry acids and bases
The Brønsted-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
Brønsted-Lowry base: any substance that accepts a proton (H+) from an acid
NaOH, NH3, KOH

5. Ammonia (NH3) + acid (HA)  ammonium ion (NH4+) + A-
Acid-base reactions
A proton is transferred from one substance (acid) to another molecule
Ammonia (NH3) + acid (HA)  ammonium ion (NH4+) + A-
Ammonia is base
HA is acid
Ammonium ion (NH4+) is conjuagte acid
A- is conjugate base

6. Water: acid or base?
Both
Products: hydronium ion (H3O+) and hydroxide

7. Amphoteric substances
Example: water
NH3 (g) + H2O(l) ↔ NH4+(aq) + OH–(aq)
HCl(g) + H2O(l) → H3O+(aq) + Cl-(aq)

8. Acid/base strength

9. Rule The stronger the acid, the weaker the conjugate base
HCl(aq) → H+(aq) + Cl-(aq)
NaOH(aq) → Na+(aq) + OH-(aq)
HC2H3O2 (aq) ↔ H+(aq) + C2H3O2-(aq)
NH3 (aq) + H2O(l) ↔ NH4+(aq) + OH-(aq)

10. Equilibrium constant
   HA  <-->   H+ + A-
Ka: >1 vs. <1

12. Expression
Molarity (M)
Normality (N)
Equivalence (N)

13. Molarity of solutions moles = grams / MW M = moles / volume (L)
grams = M x vol (L) x MW

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

15. 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

16. Exercise
What is the normality of H2SO3 solution made by dissolving 6.5 g into 200 mL? (MW = 98)?

17. But…
Molarity (and normality) is not useful for understanding neutralization reactions.
1M HCL neutralizes 1M NaOH
But…
1M HCl does not neutralize 1M H2SO3 
Why? 

18. Equivalents
The amount of molar mass (g) of hydrogen ions that an acid will donate
or a base will accept
1 mole HCl = 1 mole [H+] = 1 equivalent
1 mole H2SO4 = 2 mole [H+] = 2 equivalents

19. Examples One equivalent of Na+ = 23.1 g One equivalent of Cl- - 35.5 g
One equivalent of Mg+2 = (24.3)/2 = g

20. Exercise
calculate the number of equivalents of: 40g of Mg+2 16g of Al+3
Mg++ : 40g x (1mol/24g) x (2eq/1mol) = 3.3 eq
Al3+: 16g x (27g/1mol) x (3eq/1mol) = 1.8 eq

21. (20.1 g/1000 mEq) x (1000 mg/g) x (5 mEq /L) = 100 mg/L
Exercises
Calculate milligrams of Ca+2 in blood if total concentration of Ca+2 is 5 mEq/L. (MW = 40.1)
(20.1 g/1000 mEq) x (1000 mg/g) x (5 mEq /L) = 100 mg/L
What is the normality of H2SO3 made by dissolving 6.5g in 200 ml? equivalents? (MW = 98)

22. Examples (calculate grams)
Physiological gram
mEq/L
1 Eq
Major electrolytes ?
= 23.1 g
Na+
98-106 g
Cl- 3
(24.3)/2 = g
Mg+2
(40.1/2) = ~20.05 g
Ca2+
39.1 g K+
25-29
61 g
HCO3- 2
SO3-2 and HPO43-

23. Titration and equivalence point
The concentration of acids and bases can be determined by titration

24. Excercise
A 25 ml solution of 0.5 M NaOH is titrated until neutralized into a 50 ml sample of HCl. What is 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

25. 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

26. MacidVacid = MbaseVbase
Another method
MacidVacid = MbaseVbase

27. Note What if one mole of acid produces two moles of H+
Consider the charges (or normality)

28. Modified equation Na x Va= Nb x Vb Na = normality of acid
Va = volume of acid
Nb = normality of base
Vb = volume of base
NaOH=1
H2SO3=2
H3PO4=3

29. Exercises
If 19.1 mL of M HCl is required to neutralize 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 mL of a sulfuric acid, H2SO4, solution, what is the molarity of the sulfuric acid?

30. Ionization of water
H3O+ = H+

31. Equilibrium constant
Keq = 1.8 x M

32. Kw
Kw is called the ion product for water

34. pH

35. What is pH?

36. Exercise What is the pH of 0.01 M HCl? What is the pH of 0.01 N H2SO3?
What is the pH of a solution of 1 x HCl?

37. Acid dissociation constant
Strong acid
Strong bases
Weak acid
Weak bases

39. pKa

40. What is pKa?

42. Henderson-Hasselbalch equation

43. The equation
pKa is the pH where 50% of acid is dissociated into conjugate base

44. Buffers

45. Maintenance of equilibrium Le Châtelier’s principle

46. What is buffer?

47. Titration

48. Midpoint

49. Buffering capacity

51. Conjugate bases Acid Conjugate base CH3COOH CH3COONa (NaCH3COO) H3PO4
NaH2PO4
H2PO4- (or NaH2PO4)
Na2HPO4
H2CO3
NaHCO3

52. How do we choose a buffer?

53. 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

54. Exercise
What is the pH of a buffer containing 0.1M HF and 0.1M NaF? (Ka = 3.5 x 10-4)
What is the pH of a solution containing 0.1M HF and 0.1M NaF, when 0.02M NaOH is added to the solution?

55. At the end point of the buffering capacity of a buffer, it is the moles of H+ and OH- that are equal
Equivalence
point

56. 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.

57. Polyprotic weak acids
Example:

58. Hence

59. Excercises
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?

60. Buffers in human body Carbonic acid-bicarbonate system (blood)
Dihydrogen phosphate-monohydrogen phosphate system (intracellular)
Proteins

61. Bicarbonate buffer
CO2 + H20
H2CO3
H+ + HCO3-

62. Blood buffering CO2 + H20 H2CO3 H+ + HCO3- Blood (instantaneously)
Lungs
(within minutes)
Excretion via kidneys (hours to days)

63. Arterial blood gases (ABG)

64. Calculations…
The ratio of bicarbonate to carbonic acid determines the pH of the blood
Normally the ratio is about 20:1 bicarbonate to carbonic acid
Blood pH can be calculated from this equation:
 pH = pK + log (HCO3-/H2CO2)
pK is the dissociation constant of the buffer, 6.10
H2CO3 =0.03 x pCO2

65. Titration curve of bicarbonate buffer Note pKa

66. Why is this buffer effective?
Even though the normal blood pH of 7.4 is outside the optimal buffering range of the bicarbonate buffer, which is 6.1, this buffer pair is important due to two properties:
bicarbonate is present in a relatively high concentration in the ECF (24mmol/L)
the components of the buffer system are effectively under physiological control: the CO2 by the lungs, and the bicarbonate by the kidneys
It is an open system (not a closed system like in laboratory)

67. Open system
An open system is a system that continuously interacts with its environment.

68. Exercise H+ + HCO3-  H2CO3  CO2 + H2O
Blood plasma contains a total carbonate (HCO3- and CO2) of 2.52 x 10-2 M. What is the HCO3-/CO2 ratio and the concentration of each buffer component at pH 7.4?

69. Exercise (continued) H+ + HCO3-  H2CO3  CO2 + H2O
What would the pH be if 10-2 M H+ is added and CO2 is eliminated (closed system)?

70. Exercise (continued) H+ + HCO3-  H2CO3  CO2 + H2O
What would the pH be if 10-2 M H+ is added under physiological conditions (open system)?

71. 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)

72. Acid-Base Imbalances
pH< 7.35 acidosis
pH > 7.45 alkalosis

73. Respiratory Acidosis
H+ + HCO3-  H2CO3  CO2 + H2O

74. Respiratory Alkalosis
H+ + HCO3-  H2CO3  CO2 + H2O

75. Metabolic Acidosis
H+ + HCO3-  H2CO3  CO2 + H2O

76. Causes of respiratory acid-base disorders

77. Causes of metabolic acid-base disorders

78. Compensation
Compensation: The change in HCO3- or pCO3 that results from the primary event
If underlying problem is metabolic, hyperventilation or hypoventilation can help : respiratory compensation.
If problem is respiratory, renal mechanisms can bring about metabolic compensation.

79. Complete vs. partial compensation
May be complete if brought back within normal limits
Partial compensation if range is still outside norms.

80. Acid-Base Disorder Primary Change Compensatory Change Respiratory acidosis pCO2 up HCO3- up Respiratory alkalosis pCO2 down HCO3- down Metabolic acidosis HCO3- down PCO2 down Metabolic alkalosis HCO3- up PCO2 up

81. FULLY COMPENSATED pH pCO2 HCO3- Resp. acidosis Normal But<7.40
Resp. alkalosis
but>7.40
Met. Acidosis
but<7.40
Met. alkalosis

82. Partially compensatedpH
pCO2
HCO3-
Res.Acidosis
Res.Alkalosis
Met. Acidosis
Met.Alkalosis

83. Examples

84. Example 1
Mr. X is admitted with severe attack of asthma. Her arterial blood gas result is as follows:
pH : 7.22
PaCO2 : 55
HCO3- : 25
pH is low – acidosis
paCO2 is high – in the opposite direction of the pH.
HCO3- is Normal
Respiratory Acidosis

85. Example 2
Mr. D is admitted with recurring bowel obstruction has been experiencing intractable vomiting for the last several hours. His ABG is:
pH : 7.5
PaCO2 :42
HCO3- : 33
Metabolic alkalosis

86. Example 3
Mrs. H is kidney dialysis patient who has missed his last 2 appointments at the dialysis centre. His ABG results:
pH: 7.32
PaCO2 : 32
HCO3-: 18
Partially compensated metabolic Acidosis

87. Example 4 Mr. K with COPD.His ABG is:
pH: 7.35
PaCO2 : 48
HCO3- :28
Fully compensated Respiratory Acidosis

88. Example 5
Mr. S is a 53 year old man presented to ED with the following ABG.
pH: 7.51
PaCO2 : 50
HCO3- : 40
Metabolic alkalosis

89. Practice ABG’s pH 7.48 PaCO2 32 HCO3- 24 pH 7.32 PaCO2 48 HCO3- 25

90. Answers to Practice ABG’s
Respiratory alkalosis
Respiratory acidosis
Metabolic acidosis
Compensated Respiratory acidosis
Metabolic alkalosis
Compensated Metabolic alkalosis

91. Salivary buffers Salivary pH  6.3 Main buffers:
Bicarbonate
Phosphate
Proteins
Below pH 5.5, demineralization usually follows

92. Flow rate [H2CO3] = 1.3 mM/L –almost constant, but [HCO3-] is not
The greater the salivary flow, the more bicarbonate ions available for combining with free hydrogen ions
Normal salivary flow rates = 0.1 and 0.6 mL/minute

93. Buffering saliva
Salivary
carbonic
anhydrase