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WATER

 Very important to living organisms


 A ubiquitous substrate
 75% in bodies of water, atmosphere, ground water, plants and animals
 25% in soil
 65-75% on total human body mass
 78% on human blood
 Hkg x 65-70%= kg of H₂O in the body- determinants/Aging

A. Importance and Uses of Water


1. Acts as a medium for the digestion of food
2. Helps in the absorption of nutrients
3. Helps in excretion of waste
 H₂O- soluble substance
 Fats- accumulate u=in adipose tissue
4. Maintain body fluids and transport ions sending nerve signal to the brain
5. Main blood component for the distribution of O₂ throughout the body
6. The cells receive the nutrient from the blood in H₂O solution
7. Chemical cells of the body becomes abnormal during excessive thirst
 Psychosomatic functions are deranged
 Hysteria
 20% loss of H₂O causes death in man and animals
B. Physical, Chemical and Biological Properties of water
1. Exists in three phases (solid, liquid, gas)
 e.g ice → liquid → water
2. Colorless, odorless and tasteless
3. Tastes owes from dissolved dissolved minerals and gases
4. Its commonness and its harmlessness when taken into suggest a certain degree
of unreactiveness. It thus, acts as a medium for many reactions without
participating in them.
5. Boiling point at 100° C or 373° K at 700 torr
6. Melting point at 0°C or 273° K at 760 torr or 1 atmosphere
7. High heat capacity
 amount of heat which causes a 1° in temperature of a unit mass of a
substance (joule/kg° value= 4.184 x 103
 prevents sudden and wide fluctuations of temperature
8. High heat of fusion and vaporization
 Heat of Fusion- amount of heat required to change a unit mass of a
substance from solid to liquid phase at a given temperature
 Heat of Vaporization- amount of heat required to change a unit mass of
a substance from liquid to gas
o 2259.4 kJ/ kg
9. Ice is less dense than the liquid H₂O at 0°C
10. As a solvent
A. Polar Molecule
 Dissolved in H₂O because of hydrogen bonding
e.g.: ethanol- an alcohol has polar hydroxyl group

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B. Covalent bonds
 Broken by the strong attraction of H₂O
Ex: HCl

C. Ionic compounds
 H₂O breaks the electrostatic forces that bind ions and forms a
solution of the compound
Ex. Salt solution

D. Uncharged biomolecules
 Between a carbonyl group and H₂O
Ex. X: H, R, OH, OR, NH₂

 Between complementary base pairs

Hydrophilic

 Greek word hydr- water; philia- loving


 Atoms of the polar functional groups that combine the identical
molecules, similar molecules and/or H₂O, ionic compounds
o Example: CH₃CO₄⁻Na⁺; K⁺H₂PO₄⁻
 Polar Covalent Compounds
o Alcohol such as C₂H₅OH (ethanol)
o Ketones such as (CH₃)₂C=O (acetone)
 Sugars
o Ionic compounds (e.g. KCl)
o Amino acids, Phosphate esters
 Proteins, nucleic acids, lipids, some carbohydrates

Page | 12 , Water
Hydrophobic

 Greek word hydr- water; phobos- fear


 Non-polar compounds that are not H₂O soluble and contain
neither ions nor polar functional groups that interact with H₂O
molecule
o Example: benzene, decane, fatty acids, cholesterol

Amphiphilic

 Greek word amphis- on both sides or end; philia- loving


 Have dual properties- have both nonpolar and ionic characteristics
o Example: sodium stearate- ionic side or end is
carboxylate anion (associated to sodium cation)

 In the presence of water tends to


form micelles, in which the polar
head groups are in contact with
the aqueous environment and the
nonpolar tails are sequestered
from the water.

 used to soluble oil


o example of biomolecules: proyeinm, nucleic acids
 Amino acids (arginine, glutamate, serine)
 Phospholipid bilayer (phosphatidylserine,
phosphatidylethanolamine)
 Nonpolar HC end
C. Structure of Water
 H- 1 1s1
 O- 8 1s2 2s2 2p4

 Non-polar molecule =
CO₂
O :: C :: O
– linear
O=C=O

Bonding in H₂O molecule

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Biomolecules of hydrogen bonding

1. Hydroxyl groups in alcohols, organic acids (COOH), carbohydrates


2. Carboxyl groups in aldehydes, ketone, acids, amides and esters
3. N-H groups in amines and amides

Water is a neutral substance

The pH Scale

D. Ionization of H₂O
H₂O H⁺ + OH⁻
Equilibrium dissociation:

mass
[ ] = moles/L, m; molecular wt .
M=
VL

Keq= equilibrium constant [1.8 X 10−16 ] [55.5] = [H⁺] [OH⁻]

Keq H₂O at 25 °= 1.8 x 10−16 M 1.0 X 10−14 M= [H⁺] [OH⁻] → Keq

[H₂O]= MOLE H O / l = 1000g/ 18 = 55.5 M


2
[H⁺]= [OH⁻] = √ 1.0 X 10−14 M

Keq [H₂O] = [H⁺] [OH⁻] = 1.0 X 10−7

pH – the negative logarithm of the hydrogen ion concentration

pH = -log [H⁺]

pH of H₂O → pH= -log [1.0 x 10−7 ] = 7

ACIDS, BASES and pH

 Acids
o Sour taste
o Substances capable of donating a proton – “proton donors’
 Ex: vinegar, lemon juice, carbonated drinks
 Bases
o Bitter taste; Feel-slippery

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Substances capable of accepting a proton – “proton acceptors”
o
 Ex: Beetle nut
 Acidic Solution
o if an aqueous solution contains more H⁺ ions than OH⁻ ion
 Basic Solution
o If an aqueous solution contains more OH⁻ than H⁺

Relationship Among [H⁺] , [OH⁻] and pH at 25°C

Solution Type [H⁺] M [OH⁻] M pH value


Acidic > 1.0 x 10−7 < 1.0 x 10−7 <7.00
Neutral = 1.0 x 10−7 = 1.0 x 10−7 = 7.00
Basic < 1.0 x 10−7 > 1.0 x 10−7 >7.00

 pH of neutral solution [OH⁻] = 2.0 X 10−3 M


[H⁺]= 1.0 X 10−7 M o Keq = [H⁺] [OH⁻]
pH= -log (1.0 X 10−7 M) 1.0 X 10−14 M
=¿ ¿
= 7.0 2.0 X 10−3 M
[H⁺] = 5.0 X 10−12 M
 pH of acidic solution o pH = -log [H⁺]
[H⁺] > 1.0 X 10−7 M = -log [5.0 X 10−12 M ]
Example: = 11.30
pH = 1.0 X 10−3 M
pH = -log (1.0 X 10−3 M)  pOH
pH = -log (1.0) - log (10 ) −3
o the negative log to the
pH = 0 + 3 base of [OH⁻]
pH = 3 pOH = - log [OH⁻]
= -log [
 pH of basic solution 5.75 X 10−11 M ]
[H⁺] < 1.0 X 10−7 M = 10.24
Example:

Sample Problems

1. In a sample of lemon juice, the [H⁺]= 3.8 X 10− 4 M . Calculate the pH.
2. A commonly available window cleaning solution has a [H⁺] of 5.3 X 10−9 M . Calculate the
pH
3. A sample of freshly pressed apple juice has a pH of 3.76 calculate the [H⁺] and [OH⁻]

Conjugate Acid-Base Pair

 Acids and bases differ only in the number of protons


HA (aq) + H₂O (l) A⁻ (aq) + H₃O⁺ (aq)
acid base conjugate base conjugate acid

o HA donates p⁺ to H₂O
o H₃O donates p⁺ to A⁻ ion

Example

1. HNO₂ + H₂O NO₂⁻ + H₃O⁺


acid base conjugate base conjugate acid

2. NH₃ + H₂O NH₄ + OH⁻


base acid conjugate acid conjugate base

3. HClO₄ + H₂O H₃O⁺ + ClO₄⁻


acid base conjugate base conjugate acid

Acids Conjugate Base


HCN CN⁻

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HCl Cl⁻
CH₃OCOOH CH₃COO⁻
NH₄ NH₃
H₂CO₃ HCO₃⁻
HCO₃⁻ CO₃

Common organic acid

 Carboxylic acid (RCOOH)


 R- methyl (CH₃ -); ethyl (CH₃CH₂ -); butyl (CH₃CH₂CH₂CH₂ -)
 COOH- carboxyl group; acidic

Acids Conjugate Base


CH₃COOH CH₃COONa
Acetic acid Sodium acetate
CH₃CH₂CH₂COOH CH₃CH₂CH₂COO
Butyric acid ⁻
Butyrate ion

Common organic base

Base Conjugate acid


NH₃ C₄H₉NH₃⁺ C₄H₉NH₂
Amine Butylammonium ion Butylamine
C₄H₉NH₃Cl (CH₃)₂NH
Butylammonium chloride Dimethylamine
C₅H₅NH⁺ (CH₃CH₂)₂N
Pyridium ion Trimethylamine

Ionization of Acid and bases

Amphiprotic substance

 A substance that can act as an acid or base


 Example:water (H₂O)

acid₁ + base₂ acid₂ + base₁ → solvent


HA + SH SH₂⁺ + A⁻ → SH
HA + H₂O H₃O⁺ + A⁻ → water
HA + CH₃OH CH₃OH₂ + A⁻ → Methyl ROH
HA + CH₃COOH CH₃COOH₂ + A⁻ → glacial acetic acid

 Base dissolved in an amphiprotic solvent (SH), the solvent acts as an acid


and the resulting ionization increase the solvent anion concentration.

base₁ + acid₂ acid₁ + base₂


B + SH BH₂⁺ + S⁻
B + H₂O BH⁺ + OH⁻
B + CH₃OH BH⁺ + CH₃O
B + CH₃COOH BH⁺ + CH₃COO⁻

HA + SH SH₂⁺ + A⁻
B + SH BH⁺ + S⁻
SH₂ + S⁻ 2 SH
______________________
HA + B BH⁺ + A⁺

Ka= dissociation constant/ ionization constant


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HA H⁺ + A⁻
Ka=¿ ¿ pKa= - log Ka → measure strength of the acid

 Smaller pKa value = stronger acid


 Larger pKa value = weaker acid
o Example: HCl (strong acid); CH₃COOH (weaker acid), NH₄⁺ (very
week acid)

Ionization of pH

Calculations of pH

A. Strong Acids and Bases:


 Acids: HCl, Br, HI, HNO₃, H₂SO₄, RSO₃H
o 100% ionized
o Example: Calculate the pH of the 0.01M solution of HCl. Since the
HClis completely ionized, the [H⁺] is 0.01M or 1 x 10⁻2 M.

HCl H⁺ + Cl⁻

pH = - log [H⁺]

pH = - log [1 x 10⁻2 M]

pH= 2= acidic

 Bases: 100% ionized NaOH, Ca(OH)₂


o Example: Calculate the pH of 0.025 M HCl
Na Na⁺ + OH⁻
Kw = [H⁺] [OH]
1.0 X 10−14 M
=¿ ¿
0.025
H⁺ = 4 X 10⁻13

pH = - log [H⁺]

pH = - log [4 X 10⁻13]

pH= 2= acidic

B. Weak acids and Bases

Acids: HA: -COOH

CH₃CH₂COOH → H⁺ + CH₃CH₂COOH
Propionic acid

BH⁺ H⁺ + B

Bases: CH₃COO⁻ Na⁺


Na⁺ F⁻ anionic A⁻

NH₃
C₄H₉NH₂
C₅H₅N Uncharged B

Ionization Reaction:

Acids Bases

1. HA H⁺ + A⁻ A + H₂O HA + OH⁻

Ka = ¿ ¿ [ HA ] [OH ⁻]
Kb =
A⁻

2. BH⁺ H⁺ + B B + H₂O BH⁺ + OH⁻

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Ka = ¿ ¿ [ BH ] [OH ⁻]
Kb =
B

Pair 1 Pair 2

[ HA ] [OH ⁻] [ BH ] [OH ⁻]
KaKb= ¿ ¿ x KaKb= ¿ ¿ X = [H⁺][OH⁻] = Kw
A⁻ B

[H⁺][OH⁻] = Kw pKa + pKb = 14

EXAMPLE

A table lists the acid ionization constant of triethanolammonium ion BH⁺ as pKa=7.8. Calculate
the pKb of triethanolamine B.

pKa= 7.8
pKb=?

pKa + pKb = Kw
14 – 7.8= pKb
pKb = 6.2

Calculation of pH of:

A. Weak acids

pH from Ka value ionization constant


HA H⁺ + A⁻
At equilibrium:
[H⁺] = [A⁻]= X HA = [C-H⁺]

 Substituting to:
Ka = ¿ ¿ Ka = ¿ ¿ → Ka = ¿ ¿ → Ka = ¿ ¿ ¿

[H⁺]2 = KaC
H⁺ = √ KaC
pH= -log [H⁺]

EXAMPLE

Calculate the pH of a 0.10M solution of chloroacetic acid, Ka= 1.38 x 10-3

[H⁺] = √ KaC

= ( 1.38 x 10−3 ) (0.10 M )
pH= 1.93

B. Weak bases
pH from initial concentration C & Kb

General equation
B + H₂O HB + OH⁻

[OH ⁻]2
Kb= ¿ ¿ =
C−[ OH ]⁻

If Kb is 10⁻⁴ or smaller
[OH ⁻]2
Kb = k[OH⁻] = √ KbC
C

EXAMPLE

Calculate the pH of 0.20M solution of Pyridine Kb= 1.5 x 10⁻⁹.

[OH⁻] = √ KbC √
[OH⁻] = ( 0.20 M ) ( 1.5 X 10−9)

Page | 18 , Water
[OH⁻] = 1.73 X 10⁻⁵ = 4.76
pH = -log [OH⁻] pH + pOH = 14
= - log (1.73 x 10⁻⁵) pOH = 14 – 4.76
pOH= 9.24

C. pH of the solution containing both an acid and a base as the conjugate pair.

HENDERSON-HASSELBACH EQUATION

 used to calculate the pH of a solution containing both an acid an a base as the


conjugate acid base pairs
 the ionization constant, Ka

Ka = ¿ ¿

logKa= log [H⁺] +log ¿ ¿

-logKa= -log [H⁺] +log ¿ ¿


pH= pKa + log ¿ ¿

uses:

1. calculating [A⁻] and [HA] separately


2. calculating ratio [A⁻]/[HA]
3. preparation of the lab buffer solution

if [A⁻] = [HA] at inflection point

pH = pKa + log 1

log 1 = 0

pH= pKa

has predictive value in protonic equilibria

1. when an acid is exactly half = pKa + 0


neutralized 2. when ratio [A⁻]/ [HA] = 100 = 1
[A] = [HA] pH= pKa + log ¿ ¿
pH= pKa + log ¿ ¿ pH= pKa + log (100/1)
[1] =pKa +2
= pKa + log
[1]
3. when the ration [A⁻]/[HA]= 1:10
pH= pKa + log (1/10)
= pKa + (-1)

EXAMPLES

1. Calculate the pH of a solution that contains 0.01M o-nitrophenol (HA) and 0.02M solution
o-nitrophenolate (A⁻), pKa for o-nitophenol = 7.21

0.02 M
pH= 7.21 + log ( )
0.01 M
pH= 7.51

2. Calculate the pH of a 0.50M solution of hydroxyl ammoniumchloride (NH₃OH) + Cl⁻ that


has been 25% neutralized NaOH. The pKb for the hydroxylamine is 7.91.

3. What is the value of the ratio [A⁻]/[HA] in a solution of lactic acid at a pH of 5? pKa=3.85

4. What is the pH of a lactic acid solution that contains 60% lactate formand 40% lactic acid
undissociated form?

BUFFER SYSTEM

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 Buffer – a compound or mixture that when added to a solution, helps maintain specific pH

 Buffer solution- a solution that will resist change in pH upon the addition of small
amounts of either acid or base or if either a strong acid or a strong base were added to the
solution

Components of Buffer:

a) Weak acid and the salt of that acid


b) Weak base and the salt of that base
c) An acid salt such as potassium acid phthalate

Formation: during the titration of weak acid with a strong base during the titration of a weak
base with strong acid

 Buffer capacity- the amount of acid or base that a buffered solution can handle with only
a certain small change in pH
 The number of mole of a strong base needed to raise the pH of one (L) of
buffer by one pH.

number of equivalent of acid/base


B.C =
ΔpH x volume of buffer (L)
The pKa of an acid in a buffer (with its conjugate base) should be near as possible to the
pH at which the buffer is to operate.

EXAMPLE

An acid- conjugate pair such as acetic acid + acetate ion has an important
property.

 It resists changes in pH of a solution or it acts as a buffer

EXAMPLES

Calculate the ration in which sodium acetate and acetic acid must be mixed to give a solution
that is buffered at pH= 5.0

pH= 5.0 Ka = ¿ ¿ [H⁺]= 1 X 10⁻⁵

pKa= ? pH= -log [H⁺] Ka= antilog pKa

pKa= 4.8 [H⁺]= antilog – 5.0 Ka= 1.58 x 10⁻⁵

pH= pKa + pKb

In what molar ratio should butylamine and HCl be mixed to prepare a buffer of pH= 10.0? At M=
0.1,the pKb butylamine (B) is 3.30, and pKa for the conjugate acid [BH⁺] is 10.70.

pH= 10.0 BH⁺= 10.70 → pKa


Page | 20 , Water
pKb= 3.30 Ka = ¿ ¿

pH= -log [H⁺] [ 1 x 10−10 ] [3.30 ]


Ka =
[H⁺]= antilog pH [10.70]

[H⁺]= 1 x 10⁻10 = 3.08

METABOLIC ACIDS AND BASES

 22,000 meq acids/day


 An average rate of metabolic activity
 If dissolved at one time in unbuffered body fluids
 pH = <1 (very acidic)
 However, pH of the blood is normally maintained between 7.36-7.44
 Intracellular pH≈ 7.1 (between 6.9-7.4)
 Widest range of extracellular pH
 metabolic function of the liver, beating of the liver
 beating of heart
 conduction of neural impulses
 maintained at pH 6.8-7.8

Major Buffer systems in the Body

1. Bicarbonate- carbonic acid


 operates principally in the Extracellular fluid
2. Hemoglobin buffer system in Red blood cells
3. Phosphate buffer system in all types of cells
4. Protein buffer system of cells and plasma

Acidosis- condition when pH falls below 7.335

Alkalosis- condition under which the pH of the body rises above 7.45

a. Carbonic acid-bicarbonate conjugate Base pair


pKa= 6.4
H₂CO₃ HCO₃⁻ + H⁺
Carbonic acid carbonate

+ base H₂CO₃ + OH⁻ HCO₃⁻ + H⁺


+ ACID HCO₃ + H⁺ H₂CO₃
Range 6.4± = 5.4-7.4

Remedied by supply of CO₂ in lungs

CO₂ (g) CO₂ (aq)


Lungs blood

b. H₂CO₃ (weak acid) + NaHCO₃ salt of the weak acid

HCl enter bloodstream


HCl + NaHCO₃ → NaCl + NaHCO₃
NaOH + H₂CO₃ → H₂O + NaHCO₃

Dihydrogen Phosphate → monohydrogen phosphate


H₂PO₄⁻ -- HPO₄2⁻
Between pH 6.2 – 8.2

H⁺ + HPO₄ → H₂PO₄⁻

OH⁻ + H₂PO₄ → HPO₄2⁻ + H₂O

Phosphate Buffers

K₂HPO₄; KH₂PO₄; NaHPO₄ and NaH₂PO₄

ACID: HCl + K₂HPO₄ → KH₂PO₄ + KCl


BASE: KOH + K₂HPO₄ → K₂H₂PO₄ + H₂O

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Protein Buffers
Hemoglobin buffers: HHb + KHb
Oxyhemoglobin buffer: HHbO₂ + KHbO₂

Human Body Fluids and their Buffer Systems

Body Fluid pH Buffer System


Blood plasma 7.4 HCO₃ ⁻ proteinate HPO ₄−2
, , ,
H ₂ CO ₃ H− protein H ₂ PO ₄−1
Organic acid
H−organic acid
RBC 7.2 HCO₃ ⁻ Hb⁻ HbO ₂ ⁻ HPO ₄ ⁻
, , ,
H ₂ CO ₃ HHb HHbO₂ ⁻ H ₂ PO ₄
Organic acid
,
H −organic acid
Spinal Fluid 7.4 HCO₃ ⁻ HPO ₄ ⁻ proteinate
, ‘
H ₂ CO ₃ H ₃ PO ₄ H− protein
Urine 4.8-7.4 HPO ₄ ⁻ proteinate Organic acid
, ,
H ₂ PO ₄ H− protein H−organic acid

Page | 22 , Water

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