03 PH Acids and Basessm

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Medical Chemistry in calculations

Calculations of pH of acids, bases and salts solutions

Contents
3 CALCULATIONS OF pH OF ACID, BASE, AND SALT SOLUTIONS ..................................... 23
3.1 Acid base indicators .................................................................................................................... 24
3.2 Sample calculations with solutions ............................................................................................. 25
3.3 Exercises...................................................................................................................................... 27

3 CALCULATIONS OF pH OF ACID, BASE, AND SALT SOLUTIONS

Acids and bases are defined in 3 theories:


1. The Arrhenius theory of acids and bases: acids (HA) are substances that ionize in water to produce
hydroxonium cation H+ and acid residue A─. Bases (BOH) are compounds that ionize to produce
hydroxide anion OH─ and cation residue B+.
Example:
H2 O
HCl ↔ H+ + Cl−
H2 O
NaOH ↔ Na+ + OH−
2. The Brønsted-Lowry theory of acids and bases: acids (HA) are proton (H+) donors, and the species
that remains when a proton has been removed from the Brønsted acid is the conjugate base. Bases
(B) are proton acceptors, thus the residue of a base becomes a conjugate acid. Every Brønsted acid
has a conjugate base forming a conjugate acid-base pair. Acid-base reactions that occurs between an
acid and a base are also called protolytic chemical reactions and the acids and bases involved are
protolytes. These reactions are reversible. The function of the Brønsted acid or base will take effect
only after the connection of two conjugated systems. Free protons are not capable of existing in a
solution; acid HA1 can donate a proton in a presence of a base B1, which can accept a proton, resulting
in a new acid HA2 and a new base B2.
Example: HCl + H2 O ↔ H3 O+ + Cl− HCl is an acid (HA1);
H2O is a base (B1);
+
H3O is a conjugate acid (HA2);
Cl− is a conjugate base (B2)
3. The Lewis theory of acids and bases: acid is a substance that can accept a pair of electrons from a
donor – a base. A Lewis acid-base reaction involves the donation of a pair of electrons from one
species to another thus using a coordinate bond (dative covalent bond). The central atom is the
acceptor, and the ligands (complexing agents) are the donors of electron pairs in a coordination
complex.

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Medical Chemistry in calculations
Calculations of pH of acids, bases and salts solutions

The acidity of a solution is expressed in a pH scale as a function of hydroxonium cation


concentration, introduced by a Danish chemist Søren Peder Lauritz Sørensen:
pH= − log[H3 O+ ]
H2 O
Strong acids and bases completely dissociates in water (e.g. HA → H+ + A−), while weak acids
H2 O
and bases dissociates in water only partially (e.g. HA ↔ H+ + A− ). Water is a unique solvent, has
ability to act both as an acid and as a base. Such substances are called amphoteric substances. Water
undergoes dissociation – auto-protolysis, or auto-ionisation – to a small extent, thus producing both
hydroxonium cation as well as hydroxide anion:
H2 O + H2 O ↔ H3 O+ + OH−
Formulas for pH calculation of various solutions are listed in the table below:
solution of: formula for pH calculation
strong monoprotic acid pH = − logcHA
strong polyprotic acid pH = − log(x.cH A )
x
strong monoprotic base pH = 14 + logcB
strong polyprotic base pH = 14 + log(x.cB )
x
weak monoprotic acid pH = 1/2(pKA − logcHA )
weak monoprotic base pH = 14 − 1/2(pKB − logcB )
salt of a weak monoprotic base and a strong acid pH = 7 − 1/2(pKB + logcBA )
salt of a weak monoprotic acid and a strong base pH = 7 + 1/2(pKA + logcBA )
salt of a weak monoprotic acid and a weak monoprotic base pH = 7 + 1/2(pKA − pKB )

3.1 Acid base indicators

Acid base indicators are solutions of weak acids or bases that has distinctly different colours in its
non-ionised and ionised forms. A change in the colour of an indicator can be used to follow the progress
of an acid base reaction. Selected acid base indicators are listed in the table below:
acid base colour
indicator in acid in base pH range
Thymol blue red yellow 1.2 – 2.8
Methyl yellow red yellow 2.9 – 4.0
Bromophenol blue yellow blue 3.0 – 4.6
Methyl orange red yellow 3.1 – 4.4
Methyl red red yellow 4.4 – 6.2
Litmus red blue 4.5 – 8.3
Bromothymol blue yellow blue 6.0 – 7.6
Thymol blue yellow blue 8.0 – 9.6
Phenolphthalein colourless pink/violet 8.2 – 10.0/13.0
Thymolphthalein colourless blue 9.3 – 10.5

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Medical Chemistry in calculations
Calculations of pH of acids, bases and salts solutions

3.2 Sample calculations with solutions

Sample calculation no. 1


Calculate the pH of a gastric juice when the concentration of hydroxonium cations is 2.3x10-2 mol/dm3.

Solution:
Use the pH equation which is:
pH = − log[H3 O+ ]

pH = − log(2.3x10-2 )
pH = 1.64

The pH of a gastric juice is 1.64.

Sample calculation no. 2


How will pH be changed in 1 L of distilled water after addition of 10 mL NaOH solution with a
concentration of 1 mol/dm3?

Solution:
Neutral pH of distilled water will turn to alkaline due to the addition of a strong base. Use the pH
equation for strong monoprotic base:
pH = 14 − pOH = 14 + log cB = 14+ log[OH─ ]
To calculate the concentration of hydroxide anions, use the following equation:
cOH− = nOH− /VOH−
NaOH is a strong base and fully dissociates in water. Number of moles of hydroxide anions (nOH− ) will
be the same in the new solution of a volume of 1.01 L (1 L + 10 mL) as in the original solution of 10 mL
(0.01 L = 10-2 L). Number of moles of hydroxide anions in the original solutions are calculated from the
equation:
nOH− = nNaOH = cNaOH .VNaOH = 1.10-2 = 0.01 mol
Then solve for a concentration of hydroxide anions:
cOH− = 0.01/1.01 = 0.0099 mol/dm3
Now solve for pH:
pH = 14 + log (0.0099) = 14 + ( − 2) = 12

The pH of a NaOH solution in distilled water is 12.

25
Medical Chemistry in calculations
Calculations of pH of acids, bases and salts solutions

Sample calculation no. 3


What is the pH of a solution of ascorbic acid (vitamin C) with a concentration of 3 mmol/dm3 and
a pKA = 4.17?

Solution:
Weak monoprotic acids dissociate according the following dissociation equilibrium equation:
HA+ H2 O ↔ H3 O+ + A−
The equilibrium constant, K of the acid dissociation equation is:
[A− ].[H3 O+ ]
K= [HA].[H2 O]
, where [HA] is the concentration of the acid in equilibrium, and is equal to the

initial concentration of the acid cHA in the case of weak acid: [HA] ≈ cHA .
From the stoichiometry of the reaction we see that for every 1 mole of HA converted, 1 mole of H 3O+
and 1 mole of A− is formed: [H3 O+ ] = [A− ].
The acid dissociation constant, KA is given by
KA =K.[H2 O]
Substituting:
2
[A− ].[H3 O+ ] [A− ].[H3 O+ ] [H3 O+ ].[H3 O+ ] [H3 O+ ]
KA = K.[H2 O] = [HA].[H2 O]
.[H2 O] = [HA]
= cHA
= cHA

Rearrangement, we get:
[H3 O+ ] = √KA.cHA
Substituting for pH:
1 1 1
pH = − log[H3 O+ ] = − log√KA.cHA = − log (KA.cHA ) = − logKA − logcHA
2 2 2
1 1
pH = pKA − logcHA
2 2
Substituting:
1 1 1
pH = 2
4.17 − 2 log(0.003 mol/L) = 2.085 − 2 (−2.523) = 3.346

The pH of a solution of ascorbic acid with a concentration of 3 mmol/dm3 and a pKA = 4.17 is 3.35.

(Formula for pH calculation of weak monoprotic bases is calculated similarly, starting from dissociation
equilibrium equation:
1 1
B + H2 O ↔ BH + OH− ; and is given by: pH = 14 + 2 logcBOH − 2 pKB.)

26
Medical Chemistry in calculations
Calculations of pH of acids, bases and salts solutions

Sample calculation no. 4


Papaverine hydrochloride is a salt of a weak base (papaverine, opium alkaloid antispasmodic drug) and
a strong acid (HCl). It is approved to treat spasms of the gastrointestinal tract and may also be used as a
smooth muscle relaxant. Calculate the pH of a 205 mmol/dm3 solution with KB = 8.5x10-9.

Solution:
We note that papaverine hydrochloride is the salt formed from a strong acid and a weak base:
HA + BOH → BA + H2 O.
The initial dissociation of the salt is: BA + H2 O → B+ + A− + H2 O.
Consequently, only the weak cation of the salt will hydrolyse: B+ + H2 O ↔ BOH + H3 O+ .
The extent of the hydrolysis is very small we can approximate: cBA ≈ [B+ ]; [H3 O+ ] = [BOH].
The base hydrolysis constant is given by:
2
[BOH].[H3 O+ ] [H3 O+ ].[H3 O+ ] [H3 O+ ]
Kh,B = K.[H2 O]2 = = =
[B+ ] cBA cBA

Rearrangement, we get:
[H3 O+ ] = √Kh,B .cBA
Substituting for pH:
1 1
pH = − log[H3 O+ ] = − log√Kh,B .cBA = log Kh,B − logcBA
2 2
The base hydrolysis constant is given also by: Kh,B = Kw /KB.
Substituting:
1 K 1 1 1 1 1 1
pH = − log ( w ) − logcBA = pKw − pKB − logcBA = 7 − pKB − logcBA
2 KB 2 2 2 2 2 2

The pH of a 205 mmol/dm3 solution of papaverine hydrochloride with the KB = 8.5x10-9 is calculated as
follows:
1 1 1 1
pH = 7 − pKB − logcBA = 7 + logKB − logcBA
2 2 2 2
1 1
pH = 7 + log(8.5x10-9 ) − log(205x10-3 )
2 2
pH = 7 − 4.035 + 0.344 = 3.3

The pH of a solution of papaverine hydrochloride is 3.3.

3.3 Exercises

1. Calculate the pH and the pOH of the following solutions:


a) 0.045 mol/dm3 HCl,
b) 1x10-3 mol/dm3 HNO3

27
Medical Chemistry in calculations
Calculations of pH of acids, bases and salts solutions

c) 0.05 mol/dm3 HClO4.


a) pH = 1.35, pOH = 12.65; b) pH = 3.0, pOH = 11.0; c) pH = 1.3, pOH = 12.7

2. Calculate the concentration of the hydroxide anions in a solution containing 0.001 moles of HCl in
1 dm3. [c(OH─) = 10-11 mol/L]

3. Calculate the pH and the pOH of a solution containing 15 g of HCl and 25 g of HNO3 in a volume
of 5.4 litres. pH = 0.83

4. Calculate the dilution factor of sulphuric acid needed to change the initial pH of 1.24 to 3.34.
r = 126

5. 100 cm3 potassium hydroxide solution was added to 100 cm3 hydrochloric acid solution of pH 2.0.
The pH of the formed solution increased to 3.0. Calculate the concentration and the pH1 of the
potassium hydroxide solution, which caused the change. What will be the pH2 resulting from the re-
addition of the same potassium hydroxide solution of a volume of 100 cm3 to the existing 200 cm3
solution of pH 3.0. cKOH = 0.008 mol/L, pH1 = 11.9, pH2 = 11.3

6. Calculate the pH and the pOH of the following solutions:


a) 2x10-3 mol/dm3 NaOH,
b) 0.4 mol/dm3 KOH,
c) 10 mmol/dm3 NaOH.
a) pH = 11.3, pOH = 2.7; b) pH = 13.6, pOH = 0.4; c) pH = 12.0, pOH = 2.0

7. Topical potassium hydroxide solution of 5 % is proved to be an effective treatment of contagious


warts. Calculate the pH of this solution (Mr = 56.1056). pH = 13.95

8. Calculate the pH of a solution containing 4 mg of NaOH (Mr = 40) in a volume of 50 mL.


[pH = 11.3]

9. Sodium hydroxide solution with a volume of 50 cm3 and a concentration of 0.2 mol/L was diluted to
800 mL. Calculate the pH of a formed solution. [pH = 12.1]

10. Calculate the pH of a 0.08 % solution of sodium hydroxide. (Mr = 40). [pH = 12.3]

11. Acetylsalicylic acid (ASA or aspirin, Mr = 180.157) is an aromatic carboxylic acid (KA = 3x10-4),
and is absorbed mostly in its non-ionized form. The rate of its absorption is affected by pH.
Acidaemia increases the concentration of the non-ionized form of salicylate, which speeds up the
absorption, but also reduces its urinary excretion and potentiates the toxicity of ASA.
a) Calculate the pH of a solution containing 500 mg ASA in 50 ml of distilled water.
b) What will be the pH if an additional 950 mL of distilled water is added?
c) Decide, whether increase or decrease of the pH is observed in a diluted solution. Indicate, in which
solution is the ASA ionisation increased.
a) pH = 2.4;
b) pH = 3.04;
c) Ionised form is increased at lower acidity – in a less concentrated solution.

28
Medical Chemistry in calculations
Calculations of pH of acids, bases and salts solutions

12. Calculate the pH of ascorbic acid (vitamin C) solution with a concentration of 0.284 mol/dm3
and pKA = 4.17. pH = 2.36

13. Boric acid is applied in a very dilute solution as an eye wash with a pH = 5.28. Calculate the amount
of boric acid needed to prepare a solution (KA = 5.51x10-10). cHA = 0.05 mol/dm3

14. Ibuprofen (propionic acid derivative, Mr = 206.29) is a nonsteroidal anti-inflammatory drug with
analgesic and antipyretic properties. The pH of its saturated solution is 3.91, and the solubility is
0.010 g in 100 mL. Calculate the KA of the drug. KA = 3.16x10-5

15. Acetylcysteine (Mr (C5H9NO3S) = 163.195; pKA = 9.5 at 30 °C) is a medication used to treat
respiratory diseases with hyper-viscous mucous secretion. Calculate the pH of a solution prepared
by dilution of 1 sachet containing 600 mg in 1.5 dL of warm water. pH = 5.5

16. Calculate the pH of a solution containing 5.45 g of NH4Cl in 1 L (Mr = 54.5; pKA = 9.26).
pH = 5.13

17. Salicylic acid is a weak acid used as a key ingredient in topical products. Mass of 0.22 g anhydrous
product was obtained after drying of 100 mL of its solution with a pH 2.43. Calculate the KA of the
salicylic acid (Mr = 138.123). KA = 8.67x10-4

18. The acid dissociation constant of the acetylsalicylic acid (ASA, aspirin) is KA = 3.3x10-4. Calculate
the pH of a solution formed by dissolving two tablets of aspirin in 250 mL of distilled water. A tablet
of aspirin contains 325 mg of acetylsalicylic acid (Mr (C9H8O4) = 180.157). pH = 2.66

19. Calculate the pH of a 0.5 % solution of acetic acid (Mr = 60.05) with a density of 0.998 g/mL and a
pKA = 4.76. [pH = 2.92]

20. Calculate the KA and the pKA of a penicillin solution with a concentration of 0.040 M and the
pH = 4.70. KA = 1x10-8, pKA = 8.0

21. Codeine is an opiate used to treat pain and as a cough medicine. Calculate the KB of a 5x10-3 mol/dm3
solution with the pH = 9.95. KB = 1.59x10-6

22. Papaverine hydrochloride (pap-HCl) is a salt of a weak base and a strong acid. It is used as a smooth
muscle relaxant. Calculate the KB of a solution with the pH = 3.31 and a concentration of
205 mmol/dm3. [KB = 8.551x10-9

23. Aniline is a weak base and is forming a salt with hydrochloric acid. Calculate the pH of a 0.1 mol/L
solution with the KB = 4.27x10-10. [pH = 2.82]

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