Ionization of Weak Monoprotic Acid

- the reaction of a weak acid with water to produce an equilibrium mixture

containing hydronium ions, the discussion was limited to molecules of those
weak electrolytes which are classified as weak acids.
- There are other molecules, or weak electrolytes, which react slightly with
water to produce hydroxide ions, customarily called bases. And the most
common is ammonia.
NH3 H!H "NH# $ !H%$
- !ther molecules which react similarly with water are methylamine, &H3NH',
ethylamine, &'H(NH', and aniline, &)H(NH', but these weak electrolytes are
rarely used in inorganic chemistry.
- *f the chemical equilibrium is applied to the reaction of ammonia with water,
the ff. expression is obtained+
$
,NH # -,!H%-
,NH3-,H'!- . /e or
0here /b designates the ioni1ation constant of the weak base.
- ammonia is a weak base with an ioni1ation constant of 2.3 x 24 %($ which is
numerically almost the same as /a for acetic acid.
Ionization of Water
- water may be considered as a weak electrolyte since the purest water
obtainable will conduct an electric current to a measurable extent.
- water reacts as either acid or a base with certain anions and cations to form
con5ugate acids and bases.
- 6nder appropriate conditions water may be regarded as either an acid or base,
since it may act as either a proton donor or a proton acceptor. This is due to
the interaction of water molecules to produce an ioni1ation reaction, similar to
that of any other acid or base.
H'! H'! " H3! $ !H%$
the equilibrium expression for the ioni1ation of water is
,H 3!-,!H%$- . /e
,H'!-'$
- since the formula%weight concentration of water is 2,444723 . ((.( 8, this
9alue can be considered as a constant, which results in an expression in which
the product of the ions of water is equal to a new constant /w, or
,H3!$-,!H%$- . /e x ,H'!-'$ and ,H3!$-,!H%$-
. /e x :((.(; '$ . /w
- /w is a special ioni1ation constant, comparable to the /a and /b of a weak
acids or bases but differing in that it is an ion product in which the formal
concentration of water is treated as a constant. /w is usually referred to as the
ion product for water, and at room temperature this constant has a 9alue of 2 x
24 %2#$. Therefore, for pure water at '( $&, the H3o$ and !H%$
concentration is 2 x 24 %<$ 8.
,H3!$-,!H%$- . 2 x 24 %2#$ 8
And
,H3!$- . ,!H%$- . 2 x 24 %<$ f
- the ion product for water, /w increases with temperature as shown in Table
#.2. /w is also affected by an increasing ion concentration, but this is to be
expected since the formality of water decreases as the concentration of
dissol9ed ions increases.
Table #.2.
Temperature & /w Temperature & /w
4 4.22 x 24%2# (4 (.( x 24 %2#
23 4.(3 x 24%2# <( 2= x 24 %2#
'( 2.42 x 24%2# 244 #3 x 24 %2#
Indicators
- the pH of a solution may be determined either colorimetrically or
electrometrically, and sometimes by a combination of the two methods. The
colorimetric method makes use of certain highly colored organic compounds,
which ha9e the property of changing color when the hydronium% ion
concentration is changed o9er a certain range. These compounds are known a
acid- base indicators.
Table 4.2 Indicators
Indicator Acid
Color
Base Color pH an!e
&resol red >ed ?ellow 4.' @ 2.3
Thymol blue :acid range; >ed ?ellow 2.' @ 3.4
>ed &abbage Axtract >ed Breen '.# @ #.(
Cromphenol blue ?ellow Clue 3.4 @ #.)
Cromcresol green ?ellow Clue 3.3 @ (.#
Dethyl red >ed ?ellow #.' @ ).'
Cromcresol purple ?ellow Eurple (.' @ ).3
Cromthymol blue ?ellow Clue ).4 @ <.)
Ehenol red ?ellow >ed ).3 @ 3.#
&resol red ?ellow >ed <.' @ 3.3
Thymol blue :base range; ?ellow Clue 3.4 @ =.)
Ehenolphthalein &olorless >ed 3.3 @ 24.4
Thymolphthalein &olorless Clue =.# @ 24.(
Ali1arin yellow > ?ellow Filac 24.2 @ 2'.2
Trinitroben1ene &olorless !range 2'.4 @ 2#.4
Common " Ion #ffect
- the principle of Fe &hatelier has been stated in effect that if any system which
is in equilibrium is disturbed, the equilibrium will be read5ust in a manner so
as to minimi1e the disturbance.
$$$$
- the effect of increasing the concentration of one ion in a solution of a weak
electrolyte in order to decrease another ion of the equilibrium mixture is called
common ion effect.
#$ample%
0hat is the hydronium @ ion concentration of a 4.4(4 8 solution of acetic acid to
which has been added (.4 g of sodium acetateG
$$$
Assuming 244 per cent ioni1ation of the $$$
Fet H . hydronium @ ion concentration
4.4)2 H . acetate concentration from $$$$ $$$$
Therefore
4.4(4 @ H . the concentration from $$$$$
Then
$$$$$$$$$$$$$$$$$$$
$$$$$$$$$$$$$$$$$$$
B&ffer 'ol&tion
- is one which resists change in hydronium @ion concentration when an
appreciable amount of either a strong acid or base is added to he solution.
- Iuch a solution contains either a mixture of a weak acid and its salt, or a
mixture of a weak base and its corresponding salts.
- Axample of a buffer mixture are acetic acid with sodium acetate, and ammonia
water with ammonium chloride.
- *s a mixture of a weak electrolyte and its salt, which by common @ ion effect
maintains a nearly constant hydronium @ ion concentration, e9en when a
strong acid or base is added.
- An increase in the concentration of one of the ions results in a momentary
decrease of the other ionJ howe9er, the two ions combine to form the
undissociated electrolyte, and the original concentrations of the ions are not
greatly changed.
Ass&min! t(at a liter of sol&tion is ).* + wit( respect to acetic acid and ).* +
wit( respect to sodi&m acetate, t(en t(e (-droni&m-ion concentration ma- be
calc&lated as%
$$$$$$$$$$$$$$$$$$$$$$$
- it should be recalled hat a strong acid, e.g., hydrochloric acid, is considered as
completely ioni1ed in water solutionJ therefore, a 4.2 8 solution of H&l should
also be 4.2 8 in respect to hydronium @ions. *f, howe9er, 4.2 gfw of H&l is
added to the preceding buffer mixture, the resulting hydronium @ ion
concentration is not 4.2 8 but is approximately one four% thousandths of this
9alue, as is shown by the ff. calculations.
$$$$$$$$$$$$$$$
Therefore, after 4.2 gfw of hydrochloric acid is added to the buffer, assuming no change
in 9olume,
&oncentration of $$$$ . 4.( gfw originally present 4.2 gfw formed in the reaction
$$$$$$ . 4.) 8
&oncentration of $$$$ . 4.( gfw originally present @ 4.2 gfw $$$$$ formed in the
reaction
$$$$$$$$ . 4.# 8
Therefore
$$$$$$$$$$$$$$$$$$$$$$$$$$$$
A general formula for computing the hydronium @ ion concentration of an acid is
$$$$$$$$$$$$$$$$$$$$$$$
0here & resents formula@weight concentration and /a is the ioni1ation constant of the
acid in the buffer mixture.
A general formula for computing the hydroxide @ ion concentration of a base buffer is
$$$$$$$$$$$$$$$$
0here /b is the ioni1ation constant of the weak base.