EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS Page # 1

EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS

1. INTRODUCTION atom) of H, 35.5 gm (1 gm atom) of Cl or 8.0
(a) All chemical combinations are followed by gm. (½ gm-atom) of O or 108 gm (1 gm-atom)
the law of equivalence. of Ag.
(b) As per the law of equivalence, for the two (b) In the reaction
reacting substances A and B, the number of Mg + Cl2  MgCl 2
equivalents of A reacted = the number of 1 atom of Mg loses 2 electrons to become Mg2+
equivalents of B reacted. ion. If we start with 1 gm-atom or 1 mole or
(c) Let us consider x factor for A in the reaction 24 gm of Mg, we have NA (6.023 × 10 23)
is xA and x factor for B = xB. Let the amounts number of Mg atoms which would lose 2NA
A and B reacted are wA and wB respectively. number of electrons and form NA number of
Let the formula wt. of A and B are MA and MB Mg2+ ions. Therefore, we get 2NA number of
respectively. electrons from 24 gm of Mg. So, NA number of
24
wA electrons can be obtained from = 12 gm of
 the no. equivalents of A reacted = 2
MA Mg. Thus the equivalent weight of Mg = 12.
xA (c) So we can also define equivalent weight of
an element in otherway. Thus equivalent weight
wB of an element is that weight of the element
 the no. of equivalents of B reacted =
MB which loses or gained Avogadro number (NA) of
xB electrons.
(d) From the concept of the determination of
w A xA w B xB oxidation state of the elements, you can easily
 MA = MB calculate the number of electron transferred in
a particular process. So, you can also calculate
(d) for a couple of reaction
the amount of reactant which transferred NA
aA + bB  dD + eE x factor = x1
number of electrons. Thereby, you can find the
dD + eE  gG + hH x factor = x2
equivalent weight of the element.
If x1  x2 , the law of equivalence is followed,
(e) For example, in the reaction
but the entire calculation by equivalent concept
0 1
becomes complicated as equivalent wt. of D in 4 Na + O2 = 2 N a2 O
first reaction and second reaction are not same.
(e) To, solve the problems of stoichiometry O.S. of Na in pure state = 0
based on coupling reactions, by equivalent O.S. of Na in Na2O = +1
concept, individual step of the reactions are to  change in O.S. per gm-atom of Na = 1
be studied carefully.  no.of elect. released per g-atom of Na = NA
(f) If balanced chemical equations for the Hence, equi. wt. of Na = atomic wt of Na = 23
reactions given or if balancing of the chemical (f) For example, in the reaction
equations can be done easily, it is advisable to 0 4
follow the mole concept rather than equivalent S + O2 = S O 2
concept to eliminate mistakes. O.S. of S in pure state = 0
(g) For acid-base reactions or for single step O.S. of S in SO2 = + 4
reacti on, one can solve the probl em by  change in O.S. per gm-atom of S = 4
calculating the equivalent wts of the reactants  no.of elect. released per gm-atom of S =
and products involved, with the aid of x factors. 4NA
Hence equivalent weight of S in the given
2. DEFINITION OF EQUIVALENT WEIGHT
(a) The equivalent weight of an element is that atomic wt of S 32
reaction = = 8
weight of the element that will combine with or 4 4
replace directly or indirectly 1.0 gm (1 gm-

Power by: VISIONet Info Solution Pvt. Ltd Website : www.edubull.com Mob no. : +91-9350679141
1
EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS Page # 2

(g) Let us find the equivalent wt.of Na and S Thus, it is evident that the equivalent weight
as per definition. As per the equation given in of the substances may vary depending on the
(e),32 gm Oxygen combines with 4 × 23 gm of "x" factor.
Na
2.1 The gram-equivalent weight or gram
4  23 equivalent or simply equivalent and
 8 gm Oxygen combines with ×8 gm of Na
32 Determination of equivalent weights for
= 23 gm of Na various substances
 the equivalent weight of Na = 23 (a) Equivalent weight when expressed in grams
As per the equation given in (f) the amount we get is known as gram-equivalent
32 gm sulphur combines with 2 ×16 gm of weight.
oxygen (b) For the sake of simplicity, we introduce a
2 × 16 gm of oxygen combines with 32 gm term gram-equivalent weight, gram-equivalent
of S. or simply 1 equivalent which means equivalent
 8 gm of oxygen combines with of given substance weight in grams. Gram-
equivalent is also abbreviated as gm-equiv.
32
× 8 gm of S (c) For example,
2  16
1 equivalent of chlorine = 35.5 gm
= 8 gm of S 1 equivalent of oxygen = 8 gm
 the equivalent weight of S = 8  71 gm chlorine = 2 equivalent of chlorine
So, you must realise the importance of change  32 gm oxygen = 4 equivalent of oxygen.
in O.S. while calculating the equivalent weight. (d) The no. of equiv. of any substance
(h) Earlier we have discussed about "x" factor,
wt. of the subs tan ce in grams.
whi ch can be ap plied confi dentl y wh il e =
Equiv. wt. of the subs tan ce in grams
calculating the equival ent weight of the
substances in the redox reactions. Equivalent w
= [where w and E represent the weight
weight of element E
and equiv. wt. of the substance]
Atomic wt of the element
= (e) Equiv. wt. of any oxidant and reductant is
x factor
Mol. wt. of oxidant
Equivalent weight of compound Equiv. wt. of oxidant =
xfactor
Formula wt of the compound Mol. wt. of reduc tant
= Equiv. wt of reductant =
x factor xfactor
(i) Let us apply the formula mentioned above. Do, remember the given formula not at all
For example, in the reaction applicable in disproportionation reaction.
(f) Equiv. wt. of acid or base in a acid-base
7 2
K MnO 4  M n reaction (not the redox reaction) is
the value of x in the given equation Mol. wt. of acid
Equiv. wt of acid =
= 7 – 2 = 5 Basicity of the acid
 equiv. wt. of KMnO4 Mol. wt. of acid
The equiv. wt. of acid =
mol. wt. of KMnO 4 158 x
= = = 31.6
5 5 Mol. wt. of base
For example, in the reaction The equiv. wt of base =
acidity of base
7 4
K M nO 4  Mn O2 Mol. wt. of base
The equiv. wt. of base =
x
x = 7 – 4 = 3.
The basicity or x for acid in a acid base reaction
 equiv. wt. of KMnO4
is equal to the total number of replacable H-
mol. wt. of KMnO 4 158 atoms present in the acid. Replacable H-atoms
= = .
3 3

Power by: VISIONet Info Solution Pvt. Ltd Website : www.edubull.com Mob no. : +91-9350679141
1
 EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS Page # 3

are such type of H-atoms which are attached Now you can also calculate the equiv. wt. of
with the atoms of group VI or group VII elements, R2O3 = 46.34+8 = 54.34
viz, O, S, Se, Te and F, Cl, Br, I. Again you may calculate the equivalent wt. of
The acidity or x for base in a acid-base reaction R in otherway by applying the given concept as
is equal to the number of replacable OH groups the valency of R = 3
present in the formula unit of base.
1 FG 326  48 IJ
Thus, acidity of Al (OH)3 = 3. The acidity of
NH4OH = 1.
 The equiv. wt of R =
3 H 2 K
139
3. DETERMINATION OF EQUIVALENT WEIGHT OF = = 46.34
3
ELEMENT, ACIDIC AND BASIC OXIDES AND But this method is not convenient one to
SALT calculate the equivalent wt. of the metal in
(a) The oxidation state of the elements in the mixed oxides. There we are to use oxidation
pure state = 0. The equivalent wt of the element state instead of valency.
Atomic wt of the element (d) The equivalent weight of salt E, which is
E = not behave as oxidizing or reducing agent is
x
(b) The equivalent wt of any compound = sum given by,
of the equivalent wt of component elements or formula wt of the salt
E =
ions. total valence of designated ion
By using this relation we can calculate the For example, the equivalent wt E of Ca3(PO4)2
equivalent wt. of any acidic and basic oxide.
It is already known to us equiv wt of O = 8 formula wt of Ca3 (PO 4 ) 2 310
= =
Equiv. wt. of the other element 32 6
= 51.6 Ans.
Atomic wt of the element
= (e) Equivalent wt of an ion
x or valency of that element
For example, formula wt (or At. wt.) of ion
=
its valency
atomic wt of Fe
Equiv. wt. of Fe2O3 = + 8 4. LAW OF EQUIVALENTS AND ITS APPLICATION
3
IN THE DETERMINATION OF EQUIVALENT
56
= + 8 = 26.5 WEIGHTS OF ELEMENTS
3
4.1Law of Equivalents
For example, (a) It is in accord with the law of equivalent
75 proportion which states,
equiv. wt of As2O3 = + 8 = 33
3 "Substances (elements or compounds) combine
(c) Let us illustrate another problem : in the ratio of their gram equivalent weights or
The molecular wt. of R2O3 is 326. What is the equivalents".
equivalent wt of R ? (b) Let g1 and g2 be the weights of the two
Let. the at. wt. of R is Ar. reacting substances and E1 and E2 their equiv
 2 Ar + 48 = 326 wts.
326  48 From the law of equivalent we can write,
or Ar = = 139
2 wt of the Ist substan ce in grams
 3 × 16 gm O combines with 2×139 gm of Equiv. wt of the Ist subs tance in grams
Ar
wt of the IInd substan ce in grams
2  139 =
 8 gm O combines with × 8 gm of Ar Equiv. wt of the IInd subs tance in grams
3  16
g1 g2 g1 E1
139 or = or =
= gm of Ar = 46.34 gm of Ar E1 E2 g2 E2
3
 the equivalent wt of R = 46.34 Ans.

Power by: VISIONet Info Solution Pvt. Ltd Website : www.edubull.com Mob no. : +91-9350679141
1
 EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS Page # 4

(c) In general we can write for the two reacting  1.44 gm oxygen combines with 3.36 gm of Fe
substances X and Y as, 3.36
 8 gm oxygen combines with × 8 gm of
144
.
wt. of X Equiv wt. of X Fe = 18.67 gm of Fe
=
wt. of Y Equiv wt. of Y  equiv. wt of Fe in iron oxide = 18.67
(d) Some times the information about the
4.2 Determination of equiv. wt. of metals by
composition of the oxides of the element is
hydrogen displacement method
given indirectly. To find the equiv. wt of the
(a) The equiv wt of metals viz, K, Na, Ca, Fe,
element we are to proceed logically.
Zn, Mg, Al and Sn,
(e) When 31.6 gm of pure copper oxide are
which can displace hydrogen from any acid or
completely reduced by dry hydrogen, 7.2 gm of
from H containing compound, can only be
water are produced. Calculate the equiv. wt of
determined by this method.
copper.
(b) For example, w1 gm. of any metal displaces
wt of oxygen, w2 present in given copper oxide
w2 gm of H from an dilute acid. The,
16
w 1 Equiv. wt. of metal = 7.2 × gm = 6.4 gm
w2 = [the equiv. wt. of H = 1] 18
1
 wt of copper w1 = 31.6 – 6.4 = 25.2 gm
w1
 Equiv. wt. of metal = w Hence, equiv wt of copper
2
w1 25.2
(c) 0.224 gm of a metal when dissolved in dilute = w × 8 = × 8 = 31.5
acid liberates 285 c.c. of hydrogen, measured 2 6.4
at 17 ºC and 78 cm of mercury pressure. Find 4.4 Determination of equivalent wt. of the
the equiv. wt. of the metal. elements from their chloride formation
w1 = 0.224 (a) The equiv. wt of the element is that weight
PVM 78 0.285  2 which combines with 35.5 gm of Cl.
wt. of hydrogen, w2 = = × (b) Let, w1 gm of the element 'x' combines with
RT 76 0.082  290
w2 gm of Cl.
= 0.0246 gm.
 w2 gm Cl combines with w1 gm of X
w1 0.224
 Equiv wt of metal = = = 9.105 w1
w2 0.0246
 35.5 gm Cl combines with w × 35.5 gm of
2
4.3 Determination of equivalent wt. of
element from the oxide formation method X
(a) From the formation of oxide the equiv. wt of w1
the element can be easily determined.  The equiv. wt. of X = w × 35.5
2
(b) Let w1 gm of element X, combines with w2
gm of O. (c) Sometimes composition of the chlorides are
 w2 gm. O combines with w1 gm of X. given indirectly.
(d) The equivalent wt. of a metal is 30. What
w1
 8 gm. O combines with w × 8 gm of X volume of chlorine would be liberated at 27 ºC
2
and 750 mm pressure by 0.6 gm of the metal
[Equiv. wt. of O = 8] ? (Aq. tension at 27 ºC = 26.6 mm)
w1 Here weight of metal = W1 = 0.6gm
 equiv. wt of X = × 8.
w2 Here, wt of chlorine = w2 gm.

0.6 30 0.6  35.5

(c) From 3.36 gm of Fe, 4.80 gm of iron oxide  w 2 = 35.5 or w2 =
30
= 0.71 gm.
is obtained. What is the equivalent wt of Fe ?
In iron oxide, the amount of Fe = 3.36 gm
FG w IJ
2 RT
In iron oxide, the
= 1.44 gm.
amount of O = 4.8 – 3.36 The volume of chlorine liberated = HMK P

Power by: VISIONet Info Solution Pvt. Ltd Website : www.edubull.com Mob no. : +91-9350679141
1
 EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS Page # 5

Now putting the equiv. wt. of Cu = 32.54 in

0.082  300
relation (1)
0.71 (750  26.6)
= × = 0.2584 lit. wt of Ag
71 760 Equiv. wt of Ag = × Equiv. wt. of Cu
wt of Cu
4.5 Determination of equivalent wt. of metal
0.432
from the displacement/substitution = × 32.54 = 108.1
0.13
reactions
(a) When one metal displaces another from a
4.6 Determination of equivalent weight of metal
solution of one of its compounds, the equivalent
by double decomposition method
weight of one metal displaces the equivalent
(a) Double decomposition method is based on
weight of the other, so that of the other can
the law of equivalent. As per this law, substances
be found.
react in the proportion of their equivalent
(b) For instance, if metallic zinc or iron be added
amount. This procedure is also applicable for
to a solution of silver nitrate or copper sulphate,
nonmetallic reactants.
finely divided silver or copper is precipitated :
(b) Let us consider a reaction as
so, we can write
PmQn + ROSP  products
wt. of zn / or / Fe Let, amount of Pm Qn reacted = w1 gm
= Let, amount of RoSp reacted = w2 gm
wt of Ag
w1 Equivalent wt of Pm Q n
Equiv. wt. of zn / or / Equiv. wt. of Fe  w2 = Equivalent wt of R o Sp
=
Equiv. wt of Ag
w1 Equivalent wt of P  Equivalent wt of Q
(c) 0.13 gm of copper displaces 0.432 gm of  w =
2 Equivalent wt of R  Equivalent wt of S
silver from silver nitrate solution. 0.13 gm of
aluminium displaces 0.47 gm of copper from If w1, w2 and Equiv wt of Q, R and S are known
copper sulphate solution. While 0.13 gm of to us, we can calculate the equiv wt of P.
hydrogen is displaced by 1.17 gm of aluminium (c) Chloride of metal 'M' contains 47.23% of the
calculate from this data the equivalent weight metal. 1 gm of this metal displaced from a
of silver. compound 0.88 gm of another metal 'N'. Find
the equivalent weight of 'M' and 'N' respectively.
wt of cu Equiv. wt. of Cu Let, the equiv wts of M and N are EM and EN
= ............... (1)
wt of Ag Equiv . wt. of Ag respectively.

wt of Al Equiv. wt. of Al EM 47.23 35.5  47.23

= ............... (2)  = or EM =
wt of Cu Equiv. wt. of Cu 35.5 52.77 52.77
or EM = 31.77
wt of Al Equiv. wt. of Al
= ............... (3) EM 1
wt of H Equiv. wt. of H  EN = 0.88
Now, introducing the informations in relation (3)
or EN = 0.88 EM = 0.88 × 31.77 = 27.96
wt of Al 117
.
Equiv. wt. of Al = × 1 = = 9
wt of H 0.13
Now, introducing equiv. wt of Al = 9 in relation
(2) we get

wt of Cu
Equiv. wt of Cu = × Equiv. wt of Al
wt of Al

0.47
= × 9 = 32.54
0.13

Power by: VISIONet Info Solution Pvt. Ltd Website : www.edubull.com Mob no. : +91-9350679141
1
 EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS Page # 6

SOLVED PROBLEMS
Ex.1 In the reaction Ex.5 What weight of HNO3 is needed to convert
Br2 + Na2CO 3  NaBr + NaBrO3 + CO2 The 62 gm of P4 in H3PO4 in the reaction ?
equiv. wt. of NaBrO3 is P4 + HNO3  H3PO4 + NO2 + H2O
(A) 63 gm (B) 630 gm
Mol. wt Mol. wt Mol. wt Mol. wt (C) 315 gm (D) 126 gm
(A) (B) (C) (D)
1 10 5 4 31  4 31
Sol. The equiv. wt. of P4 = =
Sol. Per mole of the formation 54 5
NaBrO3 the x factor = + 5 62  5
 62 gm P4 = equiv. of P4
Mol. wt 31
 equiv. wt. of NaBrO3 = (Ans. C)
5 = 10 equiv. of P4
Ex.2 The equiv. wt. of hypo in the reaction Mol. wt 63
Na2 S2 O 3 + Cl2 + H2O  The equiv. wt. of HNO3 = =
1 1
Na2SO 4 + H2SO4 + HCl is –  the wt. of HNO3 required
Mol. wt Mol. wt Mol. wt Mol. wt = 10 × 63 = 630 gm (Ans. B)
(A) (B) (C) (D)
2 4 1 8 Ex.6 The equiv. wt. of an element is 9. If it
2 forms volatile chloride of vapour density 58.5.
Sol. Na 2S2 O 3 + Cl2 + H2O  What is the approximate at wt. of the element ?
6 6
(A) 9 (B) 18 (C) 27 (D) 54
Na 2 S O 4 + H2 S O 4 + HCl Sol. Let, the molecular formula of the chloride is
MClx and at wt. of the element is a
 x factor for Na2S2O3 = 2|(2 – 6)| = 8
 9x + x × 35.5 = 58.5 × 2
Mol. wt
 equiv. wt. of Na2S2O3 = (Ans.D) 58.5  2
8 x = = 2.63
44.5
Ex.3 In acting as a reducing agent, a piece of The nearest whole no. of 2.63 = 3
metal M weighing 16 grams gives up 2.25 ×  approximate at wt. of the element
1023 electrons, what is the equiv.alent weight = 9 × 3 = 27 (Ans. C)
of the metal Ex.7 6.90 gm of a metal carbonate were
(A) 42.83 (B) 21.33 (C) 83.32 (D) 32 dissolved in 60 ml of 2(N) HCl. The excess acid
Sol. NA no of electron will be removed by was neutralized by 20 ml of 1(N) NaOH. What
6.023  10 23 is the equiv.alent wt. of metal ?
× 16 gm of metal M (A) 40 (B) 20 (C) 19 (D) 39
2.25  10 23
Sol. Equiv. of HCl taken = 60 × 2 × 10–3
= 42.83 gm of metal M
Equiv. of HCl present after the reaction
 equiv. wt. of metal is 42.83
= 20 × 1 × 10–3
(Ans.A)  Equiv. of HCl utilized = 100 × 10–3
Ex.4 The equiv. wt. of the salt  100 × 10–3 equiv. of metal carbonate
KHC2O4, H2C2O4, 4H2O (to be used as a reducing = 6.90 gm
agent) is -  1 equiv. of metal carbonate
Mol. wt Mol. wt Mol. wt Mol. wt 6.90
(A) (B) (C) (D) = = 69 gm
1 2 3 4 10 1
Sol. Per moles of this salt moles of C2O42– = 2  equiv. wt. of metal = 69 – 30 = 39
 no of electrons transferred per moles of [becuase equiv. wt. of carbonate = 30]
this salt is (Ans. D)
2C2O42–  2 × 2e = 2CO2 × 2 FG NIJ FG N IJ
 'x' factor (as a reducing) of the given Ex.8 10 ml of H 2K HCl, 30 ml of H 10 K HNO3 and
salt = 4
FG NIJ
 equiv. wt. of the given salt =
Mol. wt 75 ml of H 5K HNO3 are mixed, the normality of
4 H+ in the resulting solution is-
(Ans. D) (A) 0.2 (B) 0.1 (C) 0.5 (D) 0.25

Power by: VISIONet Info Solution Pvt. Ltd Website : www.edubull.com Mob no. : +91-9350679141
1
 EQUIVALENT CONCEPT AND VOLUMENTRIC ANALYSIS Page # 7

FG NIJ
Sol. The equiv. of H+ in 10 ml of
H 2K HCl
 equiv. wt. =
126
2
= 63
10
= × 10–3
2 250 ml of seminormal solution
FG N IJ
The equiv. of H+ in 30 ml of H 10 K HNO3
=
250
× 10–3 equiv..
30 100
= × 10–3
10
FG NIJ  wt. of H2C2O4, 2H2O required
The equiv. of H+ in 75 ml of H 5K HNO3
=
250
× 10–3 × 63 gm = 0.1575 gm
100
75
= × 10–3 (Ans. B)
5
Ex.11 Which of the following has the highest
Hence, total equiv. of H+
normality ? (consider each of the acid is 100%
= (5 + 3 + 15) × 10–3 = 23 × 10–3
ionised.)
total volume of solution = 115 ml
(A) 1 (M) H2SO4 (B) 1 (M) H3PO3
Hence, normality of H+ in the resulting mixture
(C) 1 (M) H3PO4 (D) 1 (M) HNO3
23  10 3  10 3
= (N) Sol. The normality of 1(M) H2SO4 = 2(N)
115
The normality of 1(M) H3PO3 = 2(N)
FG NIJ The normality of 1(M) H3PO4 = 3(N)
= H 5K = 0.2 (N) (Ans. A)
The normality of 1(M) HNO3 = 1(N)
(Ans. C)
Ex.9 500 ml of 0.2 (M) H2SO4 are mixed with
250 ml of 0.1 (M) Ba(OH)2, the normality of Ex.12 0.45 gm of an acid of mol. wt. 90 was
resulting solution is - neutralised by 20 ml of 0.5 (N) caustic potash.
(A) 0.2 (B) 0.1 (C) 0.5 (D) 0.25 The basicity of acid is-
Sol. 500 ml of 0.2 (M) H2SO4 (A) 1 (B) 2 (C) 3 (D) 4
= 500 × 0.2 × 10–3 moles of H2SO4 Sol. 20 ml of 0.5 (N) caustic potash
= 0.5 × 0.2 × 2 equiv. of H2SO4 = 20 × 0.5 × 10–3 equiv. of caustic potash
= 0.2 equiv. of H2SO4  20 × 0.5 × 10–3 equiv. of acid = 0.45 gm
250 ml of 0.1 (M) Ba(OH)2 0.45
 1 equiv. of acid = = 45 gm
= 250 × 0.1 × 10–3 moles of Ba (OH)2 10  10 3
= 250 × 0.1 × 10–3 × 2
90
= 0.05 equiv. of Ba (OH)2  x for acid = = 2
45
 Excess H2SO4 = 0.2 – 0.05 = 0.15 equiv.
Hence, basicity of acid = 2
Hence normality of H2SO4 in resulting solution
0.15 (Ans. B)
= × 1000 = 0.2 (N) (Ans. A) Ex.13 The equivalent wt. of a metal is double
750
that of oxygen. How many times is weight of its
Ex.10 What weight of H2C2O4, 2H2O (mol. wt.
oxide greater than the wt. of metal ?
= 126) should be dissolved to prepare 250 ml of
(A) 2 (B) 3 (C) 1.5 (D) 0.25
centinormal to be used as a reducing agent ?
Sol. The equiv. wt. of the metal = 16
(A) 0.63 gm (B) 0.1575 gm
The equiv. wt. of the metal oxide
(C) 0.126 gm (D) 0.875 gm
= 16 + 8 = 24
Sol. Per mole of given acid C2O42– present
24
= 1 mole  oxide is
16
 C 2O4 2–  CO2 + 2e = 1.5 times greater than the wt. of metal
 x factor for H2C2O4, 2H2O as a reducing (Ans. C)
agent = 2

Power by: VISIONet Info Solution Pvt. Ltd Website : www.edubull.com Mob no. : +91-9350679141
1