ACID-BASE BALANCE

Plan:

1. Acids and bases: properties and strength.

2. The dissociation of water.
3. The pH scale.
4. Acid-base buffers.

By the 1884 definition of Svante Arrhenius (Sweden):

Acid is a material that can release a proton or hydrogen ion (H +).
HCl  H+ + Cl¯
Base, or alkali, is a material that can donate a hydroxide ion (OH-).
NaOH  Na+ + OH¯

By the definition of both Thomas Lowry (England) and J.N. Brensted

(Denmark):
Acid is a material that donates a proton.
Base is a material that can accept a proton.

The Lewis definitions are:

Acids are electron pair acceptors;

Bases are electron pair donors.

Each ionizable pair has a proton donor and a proton acceptor. Acids are paired with
bases. Each acid has a proton available (an ionizable hydrogen) and another part,
called the conjugate base.
HNO + H O
3 2 (NO )- + (H O)
3 3
+

CONJUGATE CONJUGATE
ACID BASE
BASE ACID
PROPERTIES OF ACIDS
For the properties of acids and bases we will use the Arrhenius definitions.

Acids release a hydrogen ion into water (aqueous) solution. You will usually see
the formula for an acid with the ionizable hydrogen at the beginning, such as HCl.

Acids neutralize bases in a neutralization reaction. An acid and a base combine

to make a salt and water. A salt is any ionic compound that could be made with the
anion of an acid and the cation of a base. The hydrogen ion of the acid and the
hydroxide ion of the base unite to form water.

Acids corrode active metals. Even gold, the least active metal, is attacked by an
acid, a mixture of acids called 'aqua regia,' or 'royal liquid.' When an acid reacts
with a metal, it produces a compound with the cation of the metal and the anion of
the acid and hydrogen gas.

Acids turn blue litmus to red. Litmus is one of a large number of organic
compounds that change colors when a solution changes acidity at a particular
point. Litmus is the oldest known pH indicator. It is red in acid and blue in base.
The phrase, 'litmus test,' indicates that litmus has been around a long time in the
English language. Litmus does not change color exactly at the neutral point
between acid and base, but very close to it. Litmus is often impregnated onto paper
to make 'litmus paper.'

PROPERTIES OF BASES
Bases release a hydroxide ion into water solution. (Or, in the Lowry - Brensted
model, cause a hydroxide ion to be released into water solution by accepting a
hydrogen ion in water.)

Bases neutralize acids in a neutralization reaction.

Where 'Y' is the anion of acid 'HY,' and 'X' is the cation of base 'XOH,' and 'XY' is
the salt in the product, the reaction is:

HY + XOH HOH + XY

Bases denature protein. This accounts for the "slippery" feeling on hands when
exposed to base. Strong bases that dissolve in water well, such as sodium or
potassium lye are very dangerous because a great amount of the structural material
of human beings is made of protein. Serious damage to flesh can be avoided by
careful use of strong bases.

Bases turn red litmus to blue. This is not to say that litmus is the only acid - base
indicator, but that it is likely the oldest one.
STRONG ACIDS AND STRONG BASES
The common acids that are almost one hundred percent ionized are:
HNO3 - nitric acid
HCl1 - hydrochloric acid
H2SO4 - sulfuric acid
HClO4 - perchloric acid
HBr1 - hydrobromic acid
HI1 - hydroiodic acid

The acids on this short list are called strong acids, because the amount of acid
quality of a solution depends upon the concentration of ionized hydrogens.

Short list of strong bases, ones that completely ionize into hydroxide ions and a
conjugate acid. All of the bases of Group I and Group II metals except for
beryllium are strong bases.

LiOH1 - lithium hydroxide

NaOH1 - sodium hydroxide
KOH1 - potassium hydroxide
RbOH1 - rubidium hydroxide
CsOH1 - cesium hydroxide
(Mg(OH)2 - magnesium hydroxide)
(Ca(OH)2 - calcium hydroxide)
(Sr(OH)2 - strontium hydroxide)
Ba(OH)2 - barium hydroxide
 WATER
The dissociation of water:
H2O  H+ + OH¯

In pure water, we can define a special equilibrium constant (Kw) as follows:

Kw = [H+][OH¯] = 1.00 · 10-14

Where Kw is the equilibrium constant for water (unitless)

[H+] is the molar concentration of hydrogen;
[OH-] is the molar concentration of hydroxide.

pH-SCALE

The acidity or basicity of a substance is defined most typically by the pH value,

defined as below:
pH = -lg[H+]

[H+][OH¯] = 1 · 10-14

At equilibrium, the concentration of H + is 10-7, so we can calculate the pH of water

at equilbrium as:

pH = -lg[H+]= -lg[10-7] = 7

Solutions with a pH of seven (7) are said to be neutral, while those with pH values
below seven (7) are defined as acidic and those above pH of seven (7) as being
basic.

pOH gives us another way to measure the acidity of a solution. It is just the
opposite of pH. A high pOH means the solution is acidic while a low pOH means
the solution is basic.

pOH = -lg[OH-]

pH + pOH = 14.00
 pH pOH
very base 14 0
13 1
base 12 2
11 3
slightly base 10 4
9 5
8 6
NEUTRAL 7 7
6 8
5 9
slightly acid 4 10
3 11
acid 2 12
1 13
very acid 0 14

pH OF STRONG ACIDS AND BASES

The concentration of a monoprotic acid is equal to the concentration of hydrogen

ion. The concentration of a monobasic alkali is equal to the concentration of
hydroxide ion.
pH = -lg[H+]
pOH = -lg[OH¯]

pH + pOH = 14

pHbase = 14 – pOH
pHbase = 14 + lg[OH¯]

What is the pH of 1·10-2 M HNO3? Nitric acid is a monoprotic strong acid. [HNO 3]
= [H+] and pH = - lg [H+], so, pH = - lg (1·10-2) = 2
What is the pH of 1·10-3 KOH? Potassium hydroxide is a monobasic strong base.
[KOH] = [OH-] and pOH = - lg [OH-] and pH = 14 – pOH. The pOH = 3 and pH =
14 – 3 = 11.

pH OF WEAK ACIDS AND BASES

The pH of weak acids:
рН = 1/2(рKа – lgСа)
The pH of weak bases:
pH = 7 + 1/2 (рKb + lgСbase)

pH values of different human organism liquids

Optimal рН Possible
Human organism liquid
values variation
Digestive juices 1,65 0,8-2,5
Urine 5,80 5,0-6,5
Large intestine juices 6,10 -
Small intestine juices 6,51 5,-7-7,07
Saliva 6,75 5,6-7,9
Gall 6,80 5,6-8,0
Blood plasma 7,40 7,36-7,44
Sweat 7,40 7,20-7,80
Cerebrospinal fluid 7,60 7,35-7,80
Lachrymal fluid 7,70 7,6-7,8
Pancreatic juice 8,80 8,6-9,0
 BUFFERS AND pH OF BUFFERS
A buffer is a solution that resists changes in pH. A buffer is made with a weak acid
and a soluble salt containing the conjugate base of the weak acid or a weak base
and a soluble salt containing the conjugate acid of the weak base.

1. Main buffers – is the mixture of weak base and its salt, formed by strong acid
(ammonia buffer NН4ОН + NН4Сl).
2. Acid buffer systems – are mixture of weak acid and its salt, formed by strong
base (acetate buffer СН3СООН + СН3СООNа, bicarbonate Н2СО3 + NаНСО3 etc).

The Henderson-Hasselbalch equation

СН3СООН СН3СОО– + Н+
СН3СООNа СН3СОО– + Nа+

[ H  ]  [CH 3COO  ]  [CH 3 COOH ]

K dis.  , then follows [ H ]  K dis. 
[CH 3COOH ] [CH 3 COO  ]

[СН3СООН] = [Acid].

[СН3СОО–] = [Salt]
[ acid ]
[ H  ]  K dis. 
[ salt ]

рН = - lg[Н+ ;

[ acid ]
pH   lg K dis .  lg ;
[ salt ]

-lgКdis. = рКа

[ acid ]
pH  ðK à.  lg
[ salt ]
 MECHANISM OF BUFFER SYSTEMS ACTION

Mechanism of buffer systems action can be observed on the example of acetic

buffer:
СН3СООН СН3СОО– + Н+
СН3СООNа СН3СОО– + Nа+
If to add comparatively small quantities of strong acid, for example НСl, to acetic
buffer there will be the following reaction:
СН3СООNа + НСl СН3СООН + NаСl
– +
СН3СОО + Н СН3СООН
Strong acid (НСl) is substituted by equivalent quantity of weak acid (СН3СООН).
On the other hand, rise of acetic acid quantity occurred in the result of adding НСl,
decreases the degree of dissociation of СН3СООН, that’s why pH of buffer
solution is not changed.
If to add strong acid to buffer solution its pH is calculated according to the
formula:
N a  Va  N HCl  V HCl
pH  ðK à  lg
N s  Vs  N HCl  VHCl
If to add some quantity of alkali to acetic buffer systems, pH of solution is also
changed a little the following reaction is:
СН3СООН + NаОН СН3СООNа + Н2О
–
СН3СООН + ОН СН3СОО– + Н2О
in result of which alkali (NаОН) is substituted by equivalent quantity of salt. In
other words, strong base is substituted by equivalent quantity of weak conjugated
base (СН3СОО–).
In the process of this reaction acid concentration is increased but pH of solution is
not changed as due to potential acidity new ions Н+ and СН3ООО– are formed.
If to add alkali pH of buffer solution is calculated according to the formula:
N a  Va  N NaOH  V NaOH
pH  ðK à  lg
N s  Vs  N NaOH  V NaOH
If to add great quantities of acid or alkali the ratio of buffer components
concentrations is changed and pH is changed more sensibly.