Potassium dichromate

Potassium dichromate, K2Cr2O7, 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. It is a
crystalline ionic solid with a very bright, red-orange color. The salt is popular in the laboratory
because it is not deliquescent, in contrast to the more industrially relevant salt sodium
dichromate.

Production
Potassium dichromate is usually prepared by the reaction of potassium chloride on sodium
dichromate. Alternatively, it can be also obtained from potassium chromate by
roasting chromite ore with potassium hydroxide. It is soluble in water and in the dissolution
process it ionizes:
K2Cr2O7 → 2 K+ + Cr2O72−
Cr2O72− + H2O ⇌ 2 CrO42− + 2 H+

Reactions
Potassium dichromate is an oxidising agent in organic chemistry, and is milder than potassium
permanganate. It is used to oxidizealcohols. It converts primary alcohols into aldehydes and,
under more forcing conditions, into carboxylic acids. In contrast, potassium permanganate tends
to give carboxylic acids as the sole products. Secondary alcohols are converted into ketones. For
example, menthone may be prepared by oxidation of menthol with acidified dichromate.[6] Tertiary
alcohols cannot be oxidized.
In an aqueous solution the color change exhibited can be used to test for distinguishing
aldehydes from ketones. Aldehydes reduce dichromate from the +6 to the +3 oxidation state,
changing color from orange to green. This color change arises because the aldehyde can be
oxidized to the corresponding carboxylic acid. A ketone will show no such change because it
cannot be oxidized further, and so the solution will remain orange.
When heated strongly, it decomposes with the evolution of oxygen.
4K2Cr2O7 → 4K2CrO4 + 2Cr2O3 + 3O2
When an alkali is added to an orange red solution containing dichromate ions, a yellow solution
is obtained due to the formation of chromate ions. For example, potassium chromate is produced
industrially using potash:
K2Cr2O7 + K2CO3 → 2 K2CrO4 + CO2
The reaction is reversible.
Treatment with cold sulphuric acid gives red crystals of chromic anhydride (CrO3):
K2Cr2O7 + 2H2SO4 → 2CrO3 + 2 KHSO4 + H2O
On heating with concentrated acid, oxygen is evolved:
2 K2Cr2O7 + 8H2SO4 → 2 K2SO4 + 2 Cr2(SO4)3 + 8 H2O + 3O2

https://en.wikipedia.org/wiki/Potassium_dichromate
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Manganese dioxide
Manganese(IV) oxide is the inorganic compound with the formula MnO2 . This blackish or brown
solid occurs naturally as the mineral pyrolusite, which is the main ore of manganese and a
component of manganese nodules. The principal use for MnO2 is for dry-cell batteries, such as
the alkaline battery and the zinc-carbon battery.[2] MnO2 is also used as a pigment and as a
precursor to other manganese compounds, such as KMnO4. It is used as a reagent in organic
synthesis, for example, for the oxidation of allylic alcohols. MnO2 in the α polymorph can
incorporate a variety of atoms (as well as water molecules) in the "tunnels" or "channels"
between the manganese oxide octahedra. There is considerable interest in α-MnO2 as a possible
cathode for lithium ion batteries.[3][4]
Several polymorphs of MnO2 are claimed, as well as a hydrated form. Like many other
dioxides, MnO2 crystallizes in the rutile crystal structure (this polymorph is called β-MnO2), with
three-coordinate oxide and octahedral metal centres.[2] MnO2 is
characteristically nonstoichiometric, being deficient in oxygen. The complicated solid-state
chemistry of this material is relevant to the lore of "freshly prepared" MnO2 in organic synthesis.
The α-polymorph of MnO2 has a very open structure with "channels" which can accommodate
metal atoms such as silver or barium. α-MnO2 is often called Hollandite, after a closely related
mineral.

Production
Naturally occurring manganese dioxide contains impurities and a considerable amount
of manganese(III) oxide. Only a limited number of deposits contain the γ modification in purity
sufficient for the battery industry.
Production of batteries and ferrite (two of the primary uses of manganese dioxide) requires high
purity manganese dioxide. Batteries require "electrolytic manganese dioxide" while ferrites
require "chemical manganese dioxide".[5]

Chemical manganese dioxide

One method starts with natural manganese dioxide and converts it using dinitrogen tetroxide and
water to a manganese(II) nitratesolution. Evaporation of the water, leaves the crystalline nitrate
salt. At temperatures of 400 °C, the salt decomposes, releasing N2O4 and leaving a residue of
purified manganese dioxide.[5] These two steps can be summarized as:
MnO2 + N2O4 ⇌ Mn(NO3)2

In another process manganese dioxide is carbothermically reduced to manganese(II)

oxide which is dissolved in sulfuric acid. The filtered solution is treated with ammonium
carbonate to precipitate MnCO3. The carbonate is calcined in air to give a mixture of
manganese(II) and manganese(IV) oxides. To complete the process, a suspension of this
material in sulfuric acid is treated with sodium chlorate. Chloric acid, which forms in situ, converts
any Mn(III) and Mn(II) oxides to the dioxide, releasing chlorine as a by-product.[5]
A third process involves manganese heptoxide and manganese monoxide. The two reagents
combine with a 1:3 ratio to form manganese dioxide:
Mn2O7 + 3 MnO → 5 MnO2

Lastly the action of potassium permanganate over manganese sulphate crystals produces the
desired oxide.[6]
2 KMnO4 + 3 MnSO4 + 2 H2O→ 5 MnO2 + K2SO4 + 2 H2SO4

https://en.wikipedia.org/wiki/Manganese_dioxide