Potassium dichromate, K

2
Cr
2
O
7
, is a common inorganic chemical reagent, most commonly
used as an oxidizing agent in various laboratory and industrial applications. As with
all hexavalent chromium compounds, it is acutely and chronically harmful to health and must be
handled and disposed of appropriately. It is a crystalline ionic solid with a very bright, red-orange
color.


Chemical Properties of Potassium Dichromate

(i) Action of heat: Potassium dichromate when heated strongly. Decomposes to give oxygen.
?
4K
2
Cr
2
O
7
(s) 4K
2
CrO
4
(s) + 2Cr
2
O
3
(s) + 3O
2

(ii) Action of acids
(a) In cold, with concentrated H
2
SO
4
, red crystals of chromium trioxide separate out.
K
2
Cr
2
O
7
(aq) + conc.H
2
SO
4
KHSO
4
(aq) + 2CrO
3
(s) + H
2
O
On heating a dichromate-sulphuric acid mixture, oxygen gas is given out.
2K
2
Cr
2
O
7
+ 8H
2
SO
4
2K
2
SO
4
+ 2Cr
2
(SO
4
)
3
+ 8H
2
O + 3O
2

(b) With HCl, on heating chromic chloride is formed and Cl
2
is liberated.
K
2
Cr
2
O
7
(aq) + 14HCl(aq) 2CrCl
3
(aq) + 2KCl(aq) + 7H
2
O + 3Cl
2
(g)
(iii) Action of alkalies: With alkalies, it gives chromates. For example, with KOH,

K
2
Cr
2
O
4
+ 2KOH 2K
2
CrO
4
+ H
2
O
orange yellow

On acidifying, the color again changes to orange-red owing to the formation of dichromate.
2K
2
CrO
4
+ H
2
SO
4
K
2
Cr
2
O
7
+ K
2
SO
4
+ H
2
O
Actually, in dichromate solution, the ions are in equilibrium with ions.
Cr
2
O
7
2
+ H
2
O 2CrO
4
2
+ 2H
+

(iv) Oxidizing nature : In neutral or in acidic solution, potassium dichromate acts as an excellent
oxidizing agent, and Cr
2
O
7
2
gets reduced to Cr
3+
. The standard electrode potential for the reaction,
Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
+3
+ 7H
2
O is + 1.31V.
This indicates that dichromate ion is a fairly strong oxidizing agent, especially in strongly acidic
solutions. That is why potassium dichromate is widely used as an oxidizing agent, for quantitative
estimation of the reducing agents such as, Fe
2+
. It oxidizes,
(a) Ferrous salts to ferric salts
K
2
CrO
7
+ 4H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 4H
2
O + 3[O]
2FeSO
4
+ H
2
SO
4
+ [O] Fe
2
[SO
4
]
3
+ H
2
O 3
K
2
Cr
2
O
7
+ 6FeSO
4
+ 7H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 3Fe
2
(SO
4
)
3
+ 7H
2
O
Ionic equation
Cr
2
O
7
2
+ 14H
+
+ 6Fe
2+
2Cr
3+
+ 6Fe
3+
+ 7H
2
O
(b) Sulphites to sulphates and arsenites to arsenates.
K
2
Cr
2
O
7
+ 4H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 4H
2
O + 3[O]
Na
2
SO
3
+ [O] Na
2
SO
4
] 3
K
2
Cr
2
O
7
+ 4H
2
SO
4
+ 3Na
2
SO
3
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 3Na
2
SO
4
+ 4H
2
O
Ionic equation
Cr
2
O
7
2
+ 8H
+
+ 3SO
3
2
2Cr
3+
+ 3SO
4
2
+ 4H
2
O
Similarly, arsenites are oxidised to arsenates.
Cr
2
O
7
2
+ 8H
+
+ 3AsO
3
3
2Cr
3+
+ 3AsO
4
3
+ 4H
2
O
(c) Hydrogen halides to halogens.
K
2
Cr
2
O
7
+ 4H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 4H
2
O + 3[O]
2HX + O H
2
O + X
2
] 3
K
2
Cr
2
O
7
+ 4H
2
SO
4
+ 6HX K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 7H
2
O + 3X
2

where, X may be Cl, Br, I.
Cr
2
O
7
2
+ 8H
+
+ 6HX 2Cr
3+
+ 3X
2
+ 7H
2
O
(d) Iodides to iodine
K
2
Cr
2
O
7
+ H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 4H
2
O + 3[O]
2KI + H
2
O + [O] 2KOH + I
2
] 3
K
2
Cr
2
O
7
+ 7H
2
SO
4
+ 6KI 4K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 3I
2
+ 7H
2
O
Ionic equation :
Cr
2
O
7
2
+ 14H
+
+ 6I

2Cr
3+
+ 7H
2
O + 3I
2

Thus, when KI is added to an acidified solution of K
2
Cr
2
O
7
iodine gets liberated.
(e) It oxidizes H
2
S to S.
K
2
Cr
2
O
7
+ 4H
2
SO
4
K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 4H
2
O + 3[O]
H
2
S + [O] H
2
O + S] 3
K
2
Cr
2
O
7
+ 4H
2
SO
4
+ 3H
2
S K
2
SO
4
+ Cr
2
(SO
4
)
3
+ 7H
2
O + 3S
Ionic equation
Cr
2
O
7
2
+ 8H
+
+ H
2
S 2Cr
3+
+ 3S + 7H
2
O
(v) Formation of insoluble chromates : With soluble salts of lead, barium etc., potassium
dichromate gives insoluble chromates. Lead chromate is an important yellow pigment.
2Pb(NO
3
)
2
+ K
2
Cr
2
O
7
+ H
2
O 2PbCrO
4
+ 2KNO
3
+ 2HNO
3

(vi) Chromyl chloride test : When potassium dichromate is heated with conc. H
2
SO
4
in the presence
of a soluble chloride salt, the orange-red vapors of chromyl chloride (CrO
2
Cl
2
) are formed.
heat

K
2
Cr
2
O
7
+ 4NaCl + 6H
2
SO
4
2KHSO
4
+ 4NaHSO
3
+ 2CrO
2
Cl
2



chromyl chloride

sup> (orange-red vapours)
Chromyl chloride vapors when passed through water give yellow-colored solution containing chromic
acid.

CrO
2
Cl
2
+ 2H
2
O 2HCl + H
2
CrO
4

Chromic acid

(yellow solution)


Chromyl chloride test can be used for the detection of chloride ion is any mixture.

Uses : Potassium dichromate is used as,
(i) An oxidizing agent
(ii) In chrome tanning
(iii) The raw material for preparing large number of chromium compounds
(iv) Primary standard in the volumetric analysis.
Structures of Chromate and Dichromate Ions
Chromates and dichromate are the salts of chromic acid (H
2
CrO
4
). In solution, these ions exist in
equilibrium with each other. Chromate ion has four oxygen atoms arranged tetrahedrally around Cr
atom. (see Fig). Dichromate ion involves a CrOCr bond as shown in Fig.



KMnO
4

Potassium permanganate is an inorganic chemical compound with the formula KMnO
4
. It is
a salt consisting of K
+
and MnO4 ions. Formerly known as permanganate of
potash or Condy's crystals, it is a strong oxidizing agent. It dissolves in water to give intensely
pink or purple solutions, the evaporation of which leaves prismatic purplish-black glistening
crystalsA permanganate is the general name for a chemical compound containing the
manganate(VII) ion, (MnO
4

). Because manganese is in the +7 oxidation state, the

permanganate(VII) ion is a strong oxidizing agent. The ion has tetrahedral
geometry.
[1]
Permanganate solutions are purple in color and are stable in neutral or
slightly alkaline media.The exact chemical reaction is dependent upon the organic contaminants
present and the oxidant utilized. For example, trichloroethene (C
2
HCl
3
) is oxidized by sodium
permanganate to form carbon dioxide (CO
2
), manganese dioxide (MnO
2
), sodium ions (Na
+
),
hydronium ions (H
+
), and chloride ions (Cl
-
)
[2]

In an acidic solution, permanganate(VII) is reduced to the colourless +2 oxidation state of
the manganese(II) (Mn
2+
) ion.
8 H+
+ MnO
4

+ 5 e

Mn
2+
+ 4 H
2
O
In a strongly basic solution, permanganate(VII) is reduced to the green +6 oxidation state of
the manganate ion, MnO
4
2
.
MnO
4

+ e

MnO
4
2

In a neutral medium however, it gets reduced to the brown +4 oxidation state
of manganese dioxide MnO
2
.
2 H
2
O + MnO
4

+ 3 e

MnO
2
+ 4 OH

Chemical Properties of Potassium Permanganate Assignment
Help
Chemical properties of Potassium Permanganate
Some important chemical reactions of KMnO
4
are given below,
Action of heat: KMnO
4
is stable at room temperature, but decomposes to give oxygen at higher
temperatures.
heat

2KMnO
4
(s) K
2
MnO
4
(s) + MnO
2
+ O
2
(g)
Oxidizing actions : KMnO
4
is a powerful agent in neutral, acidic and alkaline media. The nature of
reaction is different in each medium. The oxidising character of KMnO
4
(to be more specific, of MnO
4

) is indicated by high positive reduction potentials for the following reactions.

Acidic medium:
MnO
4

+ 8H
+
+ 5e

? Mn
2+
+ 4H
2
O E
o
= 1.51 V
Alkaline medium
MnO
4

+ 2H
2
O + 3e

? MnO
2
+ 4OH

E
o
= 1.23 V
In strongly alkaline solutions and with excess of MnO
4

, the reaction is
MnO
4

+ e

? MnO
4
2
E
o
= 0.56 V
There are a large number of oxidation-reduction reactions involved in the chemistry of manganese
compounds. Some typical reactions are,
In the presence of excess of reducing agent in acidic solutions permanganate ion gets reduced to
manganous ion, e.g.,
5Fe
2+
+ MnO
4

+ 8H
+
5Fe
3+
? Mn
2+
+ 4H
2
O
An excess of reducing agent in alkaline solution reduces permanganate ion only to manganese
dioxide e.g.,
3NO
2

+ MnO
4

+ 2OH

3NO
3

+ MnO
2
+ 4H
2
O
In faintly acidic and neutral solutions, manganous ion is oxidized to manganese oxidized to
manganese dioxide by permanganate.
2MnO
4

+ 3Mn
+2
+ 2H
2
O 5MnO
2
+ 4H
+

In strongly basic solutions, permangante oxidizes manganese dioxide to manganate ion.
MnO
2
+ 2MnO
4

+ 4OH

3MnO
4
2
+ 2H
2
O
In acidic medium, KMnO
4
oxidizes,
Ferrous salts to ferric salts
2KMnO
4
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 3H
2
O + 5[O]
2FeSO
4
+ H
2
SO
4
+ [O] Fe2(SO
4
)
3
+ H
2
O] 5
2KMnO
4
+ 8H
2
SO
4
+ 10FeSO
4
K
2
SO
4
+ 2MnSO
4
+ 5Fe
2
(SO
4
)
3
+ 8H
2
O
Ionic equation
2MnO
4

+ 16H
+
+ 10Fe
2+
2Mn
2+
+ 10Fe
3+
+ 8H
2
O
The reaction forms the basis of volumetric estimation of Fe
2+
in any solution by KMnO
4
.
Oxalic acid to carbon dioxide
2KmNO
4
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 3H
2
O + 5[O]
(COOH)
2
+ [O] 2CO
2
+ H
2
O] 3
2KMnO
4
+ 3H
2
SO
4
+ 5(COOH)
2
K
2
SO
4
+ 2MnSO
4
+ 10CO
2
+ 8H
2
O
Ionic equation
2MnO
4

+ 6H
+
+ 5(COOH)
2
2Mn
2+
+ 10CO
2
+ 8H
2
O
Sulphites to sulphates
2KMnO
4
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 3H
2
O + 5[O]
Na
2
SO
3
+ [O] Na
2
SO
4
] 5

2KMnO
4
+ 3H
2
SO
4
+ 5Na
2
SO
3
K
2
SO
4
+ 2MnSO
4
+ 5Na
2
SO
4
+ 3H
2
O
Ionic equation
2MnO
4

+ 6H
+
+ 5SO
3
2
2Mn
2+
+ 5SO
4
2
+ 3H
2
O
Iodides to iodine in acidic medium
2KMnO
4
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 3H
2
O + 5[O]
2KI + H
2
O + [O] I
2
+ 2KOH 5
2KOH + H
2
SO
4
K
2
SO
4
+ 2H
2
O] 5
2KMnO
4
+ 8H
2
SO
4
+ 10 KI 6K
2
SO
4
+ 2MnSO
4
+ 5I
2
+ 8H
2
O
Ionic equation
2MnO
4

+ 16H
+
+ 10I

2Mn
2+
+ 5I
2
+ 8H
2
O
Hydrogen peroxide to oxygen
2KMnO
4
+ 3H
2
SO
4
K
2
SO
4
+ 2MnSO
4
+ 3H
2
O + 5[O]
H
2
O
2
+ [O] H
2
O + O
2
5
2KMnO
4
+ 3H
2
SO
4
+ 5H
2
O
2
K
2
SO
4
+ 2MnSO
4
+ 8H
2
O + 5O
2

Manganous sulphate (MnSO
4
) to manganese dioxide (MnO
2
)
2KMnO
4
+ H
2
O 2KOH + 2MnO
2
+ 3[O]
MnSO
4
+ H
2
O + [O] MnO
2
+ H
2
SO
4
3
2KOH + H
2
SO
4
K
2
SO
4
+ 2H
2
O
2KMnO
4
+ 3MnSO
4
+ 2H
2
O 5MnO
2
+ K
2
SO
4
+ 2H
2
SO
4

Ionic equation
2MnO
4

+ 3Mn
2+
+ 2H
2
O 5MnO
2
+ 4H
+

Ammonia to nitrogen
2KMnO
4
+ H
2
O 2MnO
2
+ 2KOH + 3[O]
2NH
3
+ 3[O] N
2
(g) + 3H
2
O
2KMnO
4
+ 2NH
3
2MnO
2
+ 2KOH + 2H
2
O + N
2
(g)

Uses : KMnO
4
is used,
(i) As an oxidizing agent. (ii) As a disinfectant against disease-causing germs. (iii) For sterilizing wells
of drinking water. (iv) In volumetric estimation of ferrous salts, oxalic acid etc. (v) Dilute alkaline
KMnO
4
solution known as Baeyers reagent.
Structure of Permanganate Ion (MnO
4

) : Mn in MnO
4

is in +7 oxidation state. Mn
7+
exhibits
sp
3
hybridisation in this ion. The structure of MnO
4

is, shown in fig.