Electrolytes, dissociation,

acid-base equilibrium
Hydrolysis, pH
Electrolytes and non-electrolytes
Electrolytes are species which conduct electricity when dissolved in water.
Dissolution doesn’t mandatory results conductivity. Solution of NaCl
conducts electricity, solution of sugar - not

Soluble salts and strong Acids or Bases form Strong Electrolytes. Salt and strong
acids (and bases) are almost fully dissociated therefore all of the ions present
are available to conduct electricity.
HCl(s) + H2O  H3O+ + Cl-

Weak Acids and Weak Bases make Weak Electrolytes. Weak electrolytes are
partially dissociated therefore not all species in solution are ions, some
particles remain in the form of molecules. Weak electrolytes have less ions
avalable to conduct electricity.
NH3 + H2O  NH4+ + OH-
Mechanism of electrolytic dissociation
 Each molecule splits into two or more charged
particles – ions
 Salt: NaCl -> Na+ + Cl- this is always the single-step
and irreversible process:
 Na2SO4 -> 2 Na+ + SO42- - still the single-step!
 Acid, base (single basic/acidic): NaOH <-> Na+ +
OH-; HCl <-> H+ + Cl- - still single-step but
reversible process
Mechanism of electrolytic dissociation
 Acid, base (multi basic/acidic) – the process
is multi step and each step is reversible:
 H2SO4 <-> H+ + HSO4-; HSO4- <-> H++SO42-
 Ca(OH)2 <-> CaOH+ + OH-; CaOH+ <-> Ca2+
+ OH-
 The equilibrium of each step is dynamic and
can be shifted left or right
Qualitative characteristics of
dissociation
STRONG vs WEAK
_ completely ionized _ partially ionized
_ strong electrolyte _ weak electrolyte
_ ionic/very polar bonds _ some covalent bonds

Strong Acids: Strong Bases:

HClO4 LiOH
H2SO4 NaOH
HI KOH
HBr Ca(OH)2
HCl Sr(OH)2
HNO3 Ba(OH)2
 Quntitative characteristics
 Those characteristics as ‘strong’, ‘weak’ or
‘average’ are just very rough and approximate
 Another, more exact parameter(s) should be
introduced in order to classify an electrolyte
as ‘strong’ or ‘weak’
 Two parameters used for this purpose most
often: dissociation degree () and
dissociation constant (K)
 Quantitative characteristics of
dissociation
 Dissociation degree (alpha, ranged 0-1)

  > 0.3 – strong electrolyte; 0.01< <0.3 – average

electrolytes; <0.01 – weak electrolytes
 Dissociation constant (Kdis, more accurate) – product
of all equilibrium concentration in the right part by
all equilibrium concentrations in the left (next slide)
Dissociation constant
 For the reaction CH3COOH  CH3COO- + H+:
 The higher is K, the stronger is the electrolyte
 General expression:
Dissociation constant
 Important! Multistage dissociation process
is characterized by separate constants for
each dissociation stage:  
[ H ][ HSO ]
K  4
1: H2SO4  H+ + HSO4- 1
[ H SO ]
2 4

[ H  ][ SO42 ]
2: HSO4-  H+ + SO42- K2 
[ HSO4 ]
 Dissociation constants

Real dissociation constants are ranged within very wide

limits. They can be very small (like 1 x 10-10 for H2S) and
quite big (like 1.2 x 10-2 for H2SO4)
This parameter is not applied usually to the strong
electrolytes
But in case of the weak or average electrolytes it is
applied widely
Dissociation constant depends on…
 Nature of the solute and solvent
 Temperature (higher temperature usually
results in increased K)
 Does not depend on side electrolytes, ions,
molecules presence
 In contrary, dissociation degree depends on
side electrolyte, ions and molecules presence
 Relation between  and K
 Let’s consider dissociation of the weak binary electrolyte:
HA+H2O  H3O+ + A-
 Let initial concentration of HA is equal to c (obviously, init.
conc. of H3O+ and A- will be zero)
 Let dissociation degree is 
 Then the equil. conc. of H3O+ and A- will be c (both) while
the remaining conc. of HA will become c(1- )
 Let’s use these values for diss. constant calculation:
[ H 3 O  ][ A  ] cc c 2 2
K K 
[ HA] c(1   ) c(1   )

c 2 pKa = -lg(Ka) is also used quite

K
(1   ) often in the solution calculation
 Two general theoretical concenpts of
dissociation
 Classical (Arrhenius) theory of dissociation
considers two classes of electrolytes – acids and
bases. Salts are just derivatives of these compounds
 Modern (Brønsted-Lowry) theory doesn’t consider
acids and bases as separate classes but describes only
transformations of H+ ion, which determines if any
substance plays a role of acid or base
 Any compound can play any of these roles (acid can
become base and vise versa)
Acid-base equilibrium (classical)
 According to the classical Arrhenius’ theory, the
acid is a substances that generates H+ ions while
dissociation, and the base is a substance generating
OH- ions while dissociation
 HCl  H+ + Cl- - acid
 NH4OH  NH4+ + OH- - base
 There are many amphoteric compounds exhibiting
both dissociation mechanisms. Zinc “hydroxide”:
 Zn(OH)2  ZnOH+ + OH- - like a base
 Zn(OH)2  H+ + HZnO2- - like an acid
Acid-base equilibrium (modern)
 Lone Hydrogen ions do not exist by
themselves in solution. H+ is always bound
with a water molecule and forms a hydronium
ion
Acid-base equilibrium (modern)
 According to Brønsted-Lowry Theory of
Acids & Bases, there are always pairs of
conjugated acids and bases. An acid always
reacts with a base forming new acid and new
base (acid 2 and base 2)
 An acid is considered as the proton (H+)
source while a base is the proton remover
Acid-base equilibrium (modern)
 CH3COOH + H2O  CH3COO- + H3O+
acid I base I base II acid II
 Brønsted-Lowry Theory of Acids & Bases:
General Equation
Brønsted-Lowry Theory
Brønsted-Lowry Theory
Notice that water is both an
acid & a base = amphoteric
 Hydrolysis
 Water exhibits the dual (amphoteric) nature
and it can react with both acids and bases
 Hydrolysis
 Hydrolysis is a process of decomposition of
various compounds by water
 Hydrolysis is not influential for strong bases,
acids and their salts
 If an acid or a base is weak or if a salt is
formed at least by one weak agent (acid or
base), the hydrolysis becomes influential
 Hydrolysis mechanism
 Strong acid: dissociation
HCl  H+ + Cl-
 Possible interaction with water:
 H+ + H2O  H3O+ – still acts like H+ = in fact,
no interaction
 Cl- + H2O – no interaction
 Outcome – no any reactions with water
 Hydrolysis mechanism
 Strong base: dissociation
NaOH  Na+ + OH-
 Possible interaction with water:
 Na+ + H2O – no interaction
 OH- + H2O – no interaction
 Outcome – no any reactions with water
 Hydrolysis mechanism
 Salt of a strong acid and a strong base:
dissociation
NaCl  Na+ + Cl-
 Possible interaction with water:
 Na+ + H2O – no interaction
 Cl- + H2O – no interaction
 Outcome – no any reactions with water
 Hydrolysis mechanism
 A weak acid or base: dissociation
CH3COOH  CH3COO- + H+ (1)
NH4OHNH4+ + OH- (2)
 Notice that both processes are equilibrium and both are shifted
to the left side
 If any of the above ions are generated by the salt dissociation,
the hydrolysis will occur!
 Sodium acetate dissociation:
 NaCH3COO  Na+ + CH3COO- (3)
 Water dissociation: H2O  H+ + OH- (4)
 Then the ‘water-generated’ H+ will be removed by (1):
 CH3COO- (from (3)) + H+ (from (4))  CH3COOH
 Outcome: H+ from (4) are removed while OH- remain in the
system = increasing basic reaction of the solution
 Hydrolysis mechanism
 A weak acid or base: dissociation
CH3COOH  CH3COO- + H+ (1)
NH4OHNH4+ + OH- (2)
 Ammonium chloride dissociation:
 NH4Cl  NH4+ + Cl- (3)
 Water dissociation: H2O  H+ + OH- (4)
 Then the ‘water-generated’ OH- will be removed by (2):
 NH4+ (from (3)) + OH- (from (4))  NH4OH
 Outcome: OH- from (4) are removed while H+ remain in the
system = increasing acidic reaction of the solution
Hydrolysis mechanism
 Hydrolysis mechanism
 General rule: the ‘stronger’ part of the salt controls
acidity/basicity of the solution
 Salt of a strong acid and a strong base (NaCl,
CaSO4, K2SO4) = no shifts of acidity/basicity, pH is
close to neutral
 Salt of a strong acid and a weak base (NH4Cl,
FeSO4, (NH4)2SO4) = acidity/basicity shifts towards
acidic, pH < 7
 Salt of a weak acid and a strong base
(NaCH3COO, K2CO3) = acidity/basicity shifts
towards basic, pH > 7
Hydrolysis example
 Baking/washing soda
(NaHCO3/Na2CO3) – both
formed by a strong base and a
very weak acid – pH is basic =
bitter taste (anybody tasted?)
 Kitchen salt (NaCl) – both parts
are strong – no bitter/acidic
taste, pH is close to neutral
 Many mineral waters consist
massive amounts of
carbonates/hydrocarbonates and
have a bit bitter taste (if not
enriched with CO2!)
Quantitative parameters of hydrolysis
 Hydrolysis intensity can be characterized by
the constant of equilibrium named hydrolysis
constant:
NaCH 3 COO  Na   CH 3 COO   dissociation

CH 3COO   H 2 O  CH 3 COOH  OH   hydrolysis

[CH 3 COOH ][OH  ] [CH 3COOH ][OH  ]

Kh  

[CH 3COO ][ H 2 O] [CH 3 COO  ]

This concentration is a constant

and can be eliminated
Hydrolysis constant representation
 This parameter can be represented by a simpler
formula [CH 3 COOH ][OH  ]
Kh 
 Source: [CH 3COO  ]
 Now consider dissociation of water and the water
constant: H 2 O  H   OH   dissociation
[ H  ][OH  ]
K  [ H  ][OH  ]  10 14  K w
[ H 2 O]

 Kw is known as ionic product of water, it is equal to

10-14 (at 25 0C, increases with rise in temperature)
Hydrolysis constant representation
 Hydrolysis constant of a salt derived from the weak
acid and strong base can be represented also as
[CH 3COOH ][OH  ] Kw
Kh  
[CH 3COO  ] K a (acid )

 Let’s check:
Kw [ H  ][[OH  ][CH 3COOH ] [CH 3COOH ][OH  ]
Kh    

K a (acid ) [CH 3COO ][ H ] [CH 3COO  ]

 The formula is correct!

Hydrolysis constant representation
 Hydrolysis constant of a salt derived from a strong acid
and a weak base can be represented similarly as
Kw
Kh 
 What does it mean? K a (base)
 A weaker acid or base means lower Ka(acid) or Ka(base)
 lower value of Ka [fraction’s denominator!] 
higher value of Kh (remember that Kw does not change!)
 Therefore, the weaker is the ‘weak’ part of a salt, the
more intense hydrolysis will occur
 If both parts (acid and base) of a salt are weak, the
hydrolysis will be very intense and often can cause
complete decomposition of a salt by water
Checking with salts solubility table
 Importance in medicine
 Hydrolysis process are responsible for many
biochemical and chemical reactions such as:
starch, polysaccharides and regular sugar
decomposition; esters decomposition and
many other reactions occurring at normal
digestion
 Normally, hydrolysis processes are kept with
the aid of various digestion ferments
produced in the organism
Some human digestive ferments
Digestion organ Ferment Target substances
Mouth cavity, saliva Ptyalin Complex carbohydrates,
starch
Gullet (esophagus) none none
Stomach Pepsin Proteins
Stomach Lipase Fats
Duodenum Amylase Simple, complex
carbohydrates
Lipase, Bile Fats
Tripsin Peptides
Small intestine Lactose Milk sugar
Amylase, maltase Disaccharides
Aminopeptidase Peptides
 More hydrolysis usage
 It technology: hydrolysis production of
technical spirits from cellulose (products are
not drinkable, only for technical use)
 Production of synthetic monosaccharides
(fructose, glucose) from starch and/or regular
sugar
 pH
 pH is very handy way to represent the hydrogen ions
(in fact, hydronium!) concentration:
pH   lg[ H  ]
 Since Kw = 10-14, [H+]=[OH-]=10-7 for the neutral
reaction and pH = 7
 Acid reaction: [H+]>[OH-]  [H+]>10-7 and pH < 7
 Basic reaction: [H+]<[OH-]  [H+]<10-7 and pH > 7
 pH is usually ranged within 1 - 14
 pOH
 There is a conjugated parameter pOH:

pOH   lg[OH ]
 Neutral reaction: pOH = 7
 Acidic: pOH>7
 Basic: pOH <7
 pH + pOH is always 14!
 Antilogs:
 If we know pH or pOH, concentrations of H +
or OH- can be calculated as negative
antilogarithms:
[ H  ]  10  pH [OH  ]  10  pOH

 Important! All concentrations here (in pH and

pOH) are molar!
 Medical importance
 Many physiological liquids are characterized by quite
narrowly ranged ‘normal’ pH values
 pH – how to determine?

 Visually – using indicators

 (still quite approx)
 pH and indicators
 Methyl orange: Red in ‘acids’; yellow in
‘alkali’; orange ‘in between’
 Color changing pH range: 3.1 – 4.4
 Meaning that everything below 3.1 is an acid,
above 4.4 – alkali, in between – ‘neutral’
 pH and indicators
 Litmus: used mostly as an indicator paper
(red to determine bases and blue to acids)
 Color changing pH range – 4.5 – 8.3
 pH and indicators
 Phenolphthalein: colorless in the acid and
neutral solutions and pink/magenta – in the
basic
 Color changing pH range 8.2 – 10
More precise pH determination
 Portable and stationary lab pH-meters
 Some pH calculation examples
 pH of the gastric juice is 2. What is mass % of HCl?
 Solution: [ H  ]  10  pH  10 2  0.01M
 Molar mass of HCl: Mr(HCl)=36.5
 Therefore, we have a 0.01 molar solution that
contains 0.01*36.5=0.365 g of HCl in 1 liter.
Taking density of such a diluted solution as 1 g/ml,
we can take that 1 liter weighs 1000 g and mass
concentration is (0.365/1000) * 100 % = 0.0365 %
 Some pH calculation examples
 Calculate pH of the 0.05 % solution of NaOH taking
its dissociation degree 100 % and density 1 g/ml
 Solution: Let’s consider 1 liter of the solution that
weighs 1000 g. It consists 0.05 % of pure NaOH or
1000*0.05/100 = 0.5 g.
 Molar weight of NaOH Mr(NaOH) = 40, then 0.5 g
makes 0.5/40=0.0125 moles.
 So, molarity of the solution is 0.0125 and pOH=-
lg(0.0125) = 1.9. Therefore, pH = 14 – pOH = 12.1
Next topic:

Titration