EXPERIMENT A2: Determination of the formula of a hydrate

Study the following sections in "Chemistry: 7th edition by Brady, Jespersen & Hyslop:
• Hydrates p 73, 90
• Chapter 2.
• Chapter 3.

WARNING:
Wearing eye-protection and safety-clothes is compulsory.
You will not be admitted to the practical without them.

Aims of this experiment

1. To convert a hydrated salt to the anhydrous salt.

2. To use the experimental results for determining the formula of the hydrate.

Discussion

Many salts, when exposed to moist air, gain a small amount of weight due to the adsorption of
water onto the surface of the crystals. This adsorbed water can be easily removed with gentle
heating. But some salts can gain larger amounts of water by absorption, actually incorporating
the water molecules into their crystalline structure. In these salts, a definite number of water
molecules becomes associated with the positive and negative ions, and these water molecules
are firmly held within the crystal. Salts of this kind are called hydrates, or hydrate salts, and
their formulas show the fixed water content in their crystals. The formula of a hydrate of
calcium chloride, CaC12 • 4 H2O, clearly shows that four molecules of water are associated
with each formula unit of calcium chloride. Hydrates can also form when water evaporates
from a salt solution. The crystals that remain frequently contain water bound within them
(water of hydration), so the crystals are hydrates. When an aqueous solution of copper(II)
sulphate is evaporated to dryness, for example, the hydrate of copper(II) sulphate, CuSO4 • 5
H2O, is obtained as beautiful blue crystals.

You can see that the formula of a hydrate may be written showing the number of moles of
water set off from the formula of the salt and separated by a dot. The formula of the hydrate of
copper(II) sulphate shows that 5 moP of water are present for each mole of copper(II) sulphate,
and it is named copper(II) sulphate pentahydrate. Some salts can form more than one hydrate.
Cobalt(II) chloride, CoC12, forms a red hydrate with the formula CoC12 • 6 H2O and a violet
hydrate, which is CoC12 • 2 H2O. The mole ratio of water to salt is revealed in their names:

𝐶𝐶𝑎𝑎𝐶𝐶𝑎𝑎2 ∙ 6 𝐻𝐻2 𝑂𝑂 𝑐𝑐𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎(𝐼𝐼𝐼𝐼) 𝑐𝑐ℎ𝑎𝑎𝑎𝑎𝑒𝑒𝑒𝑒𝑑𝑑𝑎𝑎 ℎ𝑎𝑎𝑒𝑒𝑎𝑎ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎

𝐶𝐶𝑎𝑎𝐶𝐶𝑎𝑎2 ∙ 2 𝐻𝐻2 𝑂𝑂 𝑐𝑐𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎(𝐼𝐼𝐼𝐼) 𝑐𝑐ℎ𝑎𝑎𝑎𝑎𝑒𝑒𝑒𝑒𝑑𝑑𝑎𝑎 𝑑𝑑𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎

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 Most hydrates will lose their water of hydration when heated strongly, leaving the anhydrous
(water-free) salt behind. Some hydrates display a colour change as the water is lost.

∆ ,−4 𝐻𝐻2 𝑂𝑂 ∆ ,−2 𝐻𝐻2 𝑂𝑂

𝐶𝐶𝑎𝑎𝐶𝐶𝑎𝑎2 ∙ 6 𝐻𝐻2 𝑂𝑂 �⎯⎯⎯⎯⎯� 𝐶𝐶𝑎𝑎𝐶𝐶𝑎𝑎2 ∙ 2 𝐻𝐻2 𝑂𝑂 �⎯⎯⎯⎯⎯� 𝐶𝐶𝑎𝑎𝐶𝐶𝑎𝑎2
red violet blue

The loss of water by a hydrate is reversible. If the anhydrous salt is exposed to moist air or some
other source of water, it will regain the water of hydration. The property of reversibility can be used
to distinguish true hydrates from other compounds that produce water when heated. The hydrate can
be reformed from the anhydrous salt by addition of water. Other substances that produce water when
heated strongly may do so because of extensive decomposition, with water simply a product of the
decomposition. Adding water to the decomposition products will not reform the original substances;
thus, they are not hydrates.

The absorption of water by an anhydrous salt may occur slowly, but their great affinity for water
allows these substances to be used as scavengers of small amounts of water in storage containers,
gases, and organic liquids (in which they are insoluble). When used to absorb water, anhydrous salts
are called desiccants (to dry). Desiccants are hygroscopic (water-attracting) substances. Some
desiccants have such a high affinity for water that they can dissolve in their own water of hydration.
Salts displaying this property are termed deliquescent (to melt from). Calcium chloride is
deliquescent and if left in contact with moist air, will absorb enough water to dissolve itself in time.

In this experiment, you are to determine the percent water in a hydrate obtained from your
demonstrator. The basic theory for doing this is described below. If your experimental work and
calculations yield an acceptable percent value, you will be given the general formula of the hydrate
as "salt. X H20." With this formula and the percent water you determined, you can calculate the value
of X and complete the formula of the hydrate. The following equations summarize the calculations
required in this experiment:

1. Calculating the Percent Water in a Hydrate

The percent water (by mass) in a hydrate is determined by dividing the mass of water lost by the
hydrate with heating by the mass of the original hydrate sample. Multiplying this fraction by 100%
will give the percent water in the hydrate.

First, determine the mass of the hydrate sample:

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 = (𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑐𝑐𝑒𝑒𝑎𝑎𝑐𝑐𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑎𝑎𝑒𝑒𝑑𝑑 + ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎) − (𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑐𝑐𝑒𝑒𝑎𝑎𝑐𝑐𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑎𝑎𝑒𝑒𝑑𝑑)

Second, after the final heating determine the mass of water lost:

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

= (𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑐𝑐𝑒𝑒𝑎𝑎𝑐𝑐𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑎𝑎𝑒𝑒𝑑𝑑 + ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎) − (𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑐𝑐𝑒𝑒𝑎𝑎𝑐𝑐𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑎𝑎𝑒𝑒𝑑𝑑
+ 𝑎𝑎𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎)

Then, calculate the mass percent water in the original hydrate:

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

% 𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 = × 100%
𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑒𝑒𝑒𝑒𝑎𝑎𝑎𝑎

2. Calculating the Formula of a Hydrate

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Now you must calculate the value of X in the formula of the hydrate, salt • X H20. X is
determined by dividing the number of moles of water lost by the hydrate sample by the
number of moles of salt in the sample. Since this is the moles of salt without the water of
hydration, it will be called the anhydrous salt. Your instructor will give you the formula of the
anhydrous salt, and from this you can calculate its molar mass by summing the molar masses
of all the atoms in the formula. Remember, the molar mass of a substance is the mass of one
mole of the species in grams. Knowing the molar mass, you can convert the mass of the
anhydrous salt to moles of anhydrous salt. The molar mass of water, H2O, is 18.0 g/mol:

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑎𝑎𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

= (𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑐𝑐𝑒𝑒𝑎𝑎𝑐𝑐𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑎𝑎𝑒𝑒𝑑𝑑 + 𝑎𝑎𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎) − (𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑐𝑐𝑒𝑒𝑎𝑎𝑐𝑐𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 + 𝑎𝑎𝑒𝑒𝑑𝑑)

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑎𝑎𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑎𝑎𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 =
𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑎𝑎𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 𝑑𝑑𝑒𝑒𝑒𝑒𝑣𝑣𝑎𝑎𝑒𝑒 𝑎𝑎𝑜𝑜𝑜𝑜

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 𝑒𝑒𝑒𝑒 ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑒𝑒𝑒𝑒𝑎𝑎𝑎𝑎 =
𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒

𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑙𝑙𝑎𝑎𝑎𝑎𝑎𝑎𝑒𝑒 𝑒𝑒𝑒𝑒 ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑒𝑒𝑒𝑒𝑎𝑎𝑎𝑎

𝑋𝑋 =
𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑜𝑜 𝑎𝑎𝑒𝑒ℎ𝑑𝑑𝑑𝑑𝑒𝑒𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 𝑒𝑒𝑒𝑒 𝑎𝑎𝑎𝑎𝑒𝑒𝑒𝑒𝑎𝑎𝑎𝑎

The formula of the hydrate is then (salt) ∙ X H2O.

Apparatus required
- crucible and lid - asbestos mat (black) / cork mat
- crucible tongs - Bunsen burner
- pipe-clay triangle - desiccator
- tripod stand - spatula

Reagents required Hydrate (given)

Procedure
1. Set up apparatus for heating a clean, empty crucible – see diagram on p 3. (See "Techniques
required", Introductory Practical Notes, pp 14-15, no 1 and 2)

2. Heat the crucible and lid gently at first with a small flame, and later with an intense flame to
red heat for 5-10 minutes.
NB: Remember to keep the Bunsen burner on the asbestos mat at all times!

3. Turn off the gas supply and allow the crucible and lid to cool off on the pipe-clay triangle for
about a minute. Then place the crucible and lid in a desiccator (communal cupboard) to cool
off completely (about 15-20 minutes). Handle crucible and lid ONLY with crucible tongs.
NB: Since warmed air expands, the desiccator lid must be left open very slightly for a
while, or it may be blown off as a result of increased internal pressure.

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Heating of the crucible and lid

4. Accurately determine the mass of the empty crucible and lid (use the electronic balance).
Record this mass correctly on the answer sheet.

5. Transfer roughly 3 g (not more!) of the given hydrate to the crucible. Record the mass (of
crucible + lid + hydrate) accurately on the answer sheet.

6. Return to your workbench and heat the crucible with its lid and contents carefully over a small
flame for about 5 minutes, and then again, with a hotter flame (depending on the type of
hydrate). After an additional 5 minutes, the crucible lid should be tilted slightly to one side.

7. Continue heating for 10-15 minutes more and then place the crucible, with its lid on, in a
desiccator to cool off completely (as in step 3).

8. Return to the electronic balance and accurately determine the mass of the crucible, lid and
residue. Record this mass on the answer sheet.

9. Using these experimental results, determine the formula of the hydrate (Assignment 1, see
answer sheet).

10. WASTE DISPOSAL

• Using a spatula, scrape out the anhydrous residue from the crucible into the labelled
beaker on the front bench.
• Then wash the crucible and lid with soap and water as usual.

REPORT

Assignment 1: Use the experimental results to determine the formula of the hydrate – use the
Answer Sheet at the end of the practical.
Assignment 2: Answer the questions for Assignment 2 on the Answer sheet at the end of the
practical.

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The following information must be completed at the top of page of the report:
• Initials and surname • Student number
• Date on which practical was done • Practical Group
• Practical Session (morning/afternoon) • Demonstrator

Completion of practical:

Have you: Done?

correctly disposed of all waste?
washed all apparatus you have used?
packed the Bunsen burner, tripod and asbestos mat (black) and
desiccator back into the "communal" cupboard?
packed the other apparatus correctly in your own cupboard?
checked that water and gas taps are properly closed?
cleaned and dried your working surface?
replaced your laboratory stool?
had your work signed by your demonstrator?

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