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The Fundamental Laws of Chemistry

As we have discussed, matter can be classified into different categories ba


sed on directly observable properties, be they physical or chemical.

Heterogeneous systems contain multiple phases and can be separated using fairl
y standard techniques (e.g., filtration, separatory funnel, etc.) into a series of homogene
ous systems. These homogeneous systems can be further classified according to whether
they are solutions, containing multiple components, or pure substances. Solutions,
themselves, can be further separated into their constituent components, although the
techniques to achieve this separation (e.g., distillation, chromatography) are somewhat more
complex than those required to separate heterogeneous systems.

Pure Substances fall into one of two categories; those which are compounds and those
which are elements. Compounds can be broken-down via some standard physical or
chemical method, elemental substances cannot. This level of "separation" is
significantly more difficult than required of the previous two levels of separation. Lavoisier
used strong heating in the presence of Iron to break-down Water, and, thus, demonstrate its
compound nature. Water can also be broken-down using electrolysis, where it is decompos
ed directly into hydrogen and oxygen gases.

It has been found there are ~115 chemically elemental substances; each represented in the
Periodic Table of the Elements.

At this point, we wish to consider the "rules," or Natural Laws, governing the reconstruction
of Compounds from the Elements. These are the Fundamental Laws of Chemistry.
Recall, Laws of Nature are broad statements to which there are no exceptions. The Laws we
will discuss are the Fundamental Laws on which the science of chemistry is built
.
The central question we wish to answer is, how can such a limited number of elemental
substances be combined such as to form the ~15 million known compounds? For
concreteness, consider the combination of elemental Carbon and elemental Oxygen by
direct chemical reaction. If the reaction is carried out in an excess of oxygen, in other words,
in a furnace with adequate ventilation, the compound Carbonic Acid is formed:
On the other hand, if the oxygen is fed into the furnace in limited amounts, via a Regulator
, the compound Carbonic Oxide is formed: How do we know these gaseous products are
indeed different compounds? The intensive physical properties of each gas are distinct:

Carbonic Acid Carbonic Oxide


Colorless Colorless
Odorless Odorless
sublimation pt. = -78o C melting pt. = -205oC boiling pt. = -191oC
Soluble in Water Insoluble in Water
Non-Combustible Combustible

Now, back to the question posed above. How can these two elements form two different
compounds? The Fundamental Laws of Chemistry will provide an answer to this question.
Further, we shall see these Laws led directly to a statement of the Atomic
Theory. This Atomic Theory provides the definitive explanation for why two different
compounds can be formed from these two elements.
Law of Conservation of Mass

The first of these Fundamental Laws to be discovered was the Law of Conservat
ion of Mass: The total mass of material present after a chemical reaction is the same as
before thereaction.

This Law was discovered by Antoine Lavoisier in about 1789. In a turn about of the Scie
ntific Method, Lavoisier had always assumed this Law was true, and sought out experiments
which would verify his assumptions. As a result of numerous combustion experiments
conducted on systems in closed containers, so as to retain any gases present, Lavoisier was
able to unambiguously verify his assumptions and formally state the Law of Conservati
on of Mass. For an example, consider our combustion reactions of elemental Carbon. If the
mass of the gasses are accounted for, it is found:

Carbon + Oxygen Carbonic Acid


Before Rxn: 1.00g 2.66g = 3.66g
After Rxn: 0.00g 0.00g 3.66g = 3.66g

Carbon + Oxygen Carbonic Oxide


Before Rxn: 1.00g 1.66g = 2.66g
After Rxn: 0.00g 0.00g 2.66g = 2.66g

Of course, these results require that each reactant be present in perfectly balanced
amounts, such that the full quantity of each is consumed completely during the reaction. If
this is not the case, some of the reagent in excess will remain at the conclusion of the
reaction. How ever, the Law of Conservation of Mass will still apply.

Hydrogen + Oxygen Water


Before Rxn: 2.00g 10.00g = 12.00g
After Rxn: 0.74g 0.00g 11.26g = 12.00g

From this example, we see a total of 12.00g of material is present both before and af
ter the chemical reaction occurs, with some of the hydrogen reagent remaining as ex
cess. Further, we can also note that oxygen is the Limiting Reagent in carrying out this reacti
on; it limits the production of water. If more oxygen were present, a greater amount of
water would be produced.

Finally, once this Law is accepted, it can be used to predict the amount of an "unseen"
reactant consumed or produced without direct measurement. For instance, when iron burns
in the air, its mass is seen to increase:

Iron + Oxygen Iron Oxide


Before Rxn: 5.00g ?g
After Rxn: 0.00g 0.00g 7.15g

From these results we can calculate the mass of oxygen needed to carry-
out the complete combustion of 5.00g of iron:
mass Oxygen = 7.15g - 5.00g = 2.15g

Finally, it must be noted the Law of Conservation of Mass, though a Fundamental Law
of Chemistry, is not a fundamental law of nature. When an energy difference occurs dur
ing a reaction, minute amounts of mass are either gained or lost. Mass is either convert
ed to energy or energy is converted to mass. The energy-mass equivalence was first postul
ated by Einstein in his famous formula; E = mc2
. While these mass differences are not detectable by the chemist, they
are important in nuclear reactions.

Law of Definite Proportions

A chemical compound, no matter what its origin or its method of preparation, always has
the same composition; i.e., the same proportions by mass of constituent elements.
This Law, sometimes known as the Law of Definite Composition, was first enuncia
ted by Joseph Proust in 1799. Proust discovered this law while analyzing samples of Cupric
Carbonate. He found two samples, one prepared via synthetic methods, and the other mined
naturally (Malachite Green), possessed the same composition of elemental Carbon, Oxygen
and Copper:

% Copper % Oxygen % Carbon


Synthetic Sample: 51.35% 9.74% 38.91%
Natural Sample: 51.35% 9.74% 38.91%

So, for example, if we decompose water by electrolysis and we recover the elem
ental gases hydrogen and oxygen (not a difficult task experimentally), and subsequently
measure the masses of each gas respectively, we can determine the composition of this
compound:

Water Hydrogen + Oxygen


Before Rxn: 10.00g
After Rxn: 1.12g 8.88g

This data yields an elemental composition of:


In a similar manner, from the data presented above, we can determine the elem
ental composition of the two Oxides of Carbon:

Carbonic Acid Carbonic Oxide


% Carbon 27.29 % 42.88 %
% Oxygen 72.71 % 57.12 %

Thus, we begin to see how these two compounds of carbon and oxygen differ, they differ in
their relative proportions of the two constituent elements. Each compound has a definite, wel
l defined composition, but different compounds of the same elements will have different
compositions.

The validity of the Law of Definite Proportions was firmly established by


a number experiments conducted by Jons Jakob Berzelius. To cite one example, he heated
powdered elemental lead with powdered elemental sufur, in different proportions, to form the
compound lead sulfide. In each case he found the elemental composition of the lead sulfide
remained unchanged.

Expt. #1
Lead + Sulfur  Lead Sulfide
Before Rxn: 10.00g 1.56g
After Rxn: 0.00g 0.00g 11.56g ==> % Lead = 86.5 %
% Sulfur = 13.5 %

Expt. #2
Lead + Sulfur  Lead Sulfide
Before Rxn: 10.00g 3.00g
After Rxn: 0.00g 1.44g 11.56g ==> % Lead = 86.5 %
% Sulfur = 13.5 %

Expt. #3
Lead + Sulfur  Lead Sulfide
Before Rxn: 18.00g 1.56g
After Rxn: 8.00g 0.00g 11.56g ==> % Lead = 86.5 %
% Sulfur = 13.5 %

From the results given above, we see attempts to increase the a


mount of one elemental substance, without likewise increasing the amount of the other,
simply leads to an excess of that substance remaining after the reaction, and not a change
in the composition of the compound.

It should be noted that forming a mixture, such as a solution, is a distinctly differ


ent process than the process associated with compound formation. Suppose copper and
zinc are mixed to form brass. This is a physical process rather than a chemical process.

Brass is not a compound because its physical properties (color, density, melting point, etc.)
are not distinct; their exact values depend on the proportions in which the copper and zinc
are mixed. This is very similar to mixing Table Salt and water to form a Salt-Water solution;
the salt and water can be mixed in different proportions. We would not think of Salt-Water as
a compound. When we combine, or "mix," hydrogen and oxygen to form water, the result is
a compound whose composition is fixed and whose properties are distinct.

Once accepted, this Law can be used to predict the amount of product which can be formed
from a given elemental reactant. For example, from the data cited above, we know that
Carbonic Acid is 27.29 % carbon and 72.71 % oxygen. So, how much Carbonic Acid can be
produced from 5.0g of carbon? Further, this result can be used to determine how much
oxygen would be consumed in the reaction forming this compound:

mass Oxygen = 18.32g - 5.00g = 13.32g

Law of Multiple Proportions

The Law of Multiple Proportions was enunciated by John Dalton at about the same time
he
postulated his Atomic Theory of Matter in ~1803. It was experimental results i
n the form which
suggested the validity of the Law of Multiple Proportions which provided Dalton wi
th the data
needed to formulate the Atomic Theory. This Law, therefore, is a central li
nchpin in the
development of modern chemistry.
If two elements form more than a single compound, the masses of one element combined
with a fixed mass of the second are in the ratio of small whole numbers.
This Law deals with the relationship between two compounds composed of the same eleme
nts.
Our Carbonic Acid - Carbonic Oxide example is a case in point. Both are composed of the
sa
me
two elements; carbon and oxygen. Recall, the above data showed that 1.00g of carbon wi
ll
combine with 2.66g of oxygen, in the case of Carbonic Acid, and 1.33g of oxygen in the case
of
Carbonic Oxide. Thus, the amount of carbon, in each case, is fixed at 1.00g. We can, in turn,
use this data to illustrate the application of the Law of Multiple Proportions:
As another example, it is found elemental iron combines with elemental chlorine t
o form two
different compounds; ferric chloride and ferrous chloride. The definite composition of t
hese two
compounds is:
Ferrous Chloride Ferric Chloride
% Iron 44.06 % 34.43 %
% Chlorine 55.94 % 65.57 %
This data can be used to determine the mass of chlorine per 1.00g of iron needed to
produce
these compounds. The results are:
Ferrous Chloride Ferric Chloride
mass Iron 1.00g 1.00g
mass Chlorine 1.27g 1.90g
Applying the Law of Multiple Proportions to these results, we obtain:
In the case of the Oxides of Carbon, Dalton would interpret the above results to mean tha
t
carbonic acid is composed of 2 Atoms of oxygen for every 1 Atom of carbon, and carbonic
oxide
contains 1 Atom of oxygen for every 1 Atom of carbon. In the case of the Chlorides of Ir
on, he
would conclude ferric chloride contains 3 Atoms of chlorine for every Atom of iron and fer
rous
chloride contains 2 Atoms of chlorine for 1 iron Atom.
It must be kept in mind, these results are purely experimental in nature. And yet
, they have led
directly to an Atomic interpretation for the formation of compounds. The Law of Multipl
e
Proportions, in conjunction with the other Fundamental Laws of chemistry, led direct
ly to the
postulates of the Atomic Theory of Matter.

Dalton's Atomic Theory of Matter


The enunciation of the Law of Multiple Proportions and the Atomic Theory of Matter by J
ohn
Dalton occurred, historically, at the same point in time. The experimental data le
d to both
conclusions simultaneously. Dalton's Atomic Theory consisted of five basic postul
ates:
Elements are composed of indivisible Atoms.
Atoms are alike for a given element.
Atoms for different elements differ in size and mass and other properties.
Compounds are formed from two or more Atoms of different elements.
Atoms combine in simple numerical ratios to form these compounds. These ratios are
different for different compounds.
As has been mentioned, the Oxides of Carbon are found to form from 2 Atoms versus 1
Atom of
oxygen to every Atom of carbon in the compound. In Dalton's view, these compounds could
be
represented as:
This would clearly explain the results of the Law of Multiple Proportions. Further
, since the
atoms combine without changing, losing or gaining parts, but instead by merely re
combining,
this would explain the Law of Conservation of Mass. And, since each "molecule" of Carbonic
Acid contains 2 Atoms oxygen to 1 Atom carbon, the proportions of each are always the
same
;
explaining the Law of Definite Proportions. A similar conclusion can be drawn for t
he case of
Carbonic Oxide In modern parlance, we would name the compounds Carbonic Acid and
Carbonic Oxide, Carbon Dioxide and Carbon Monoxide, respectively. Finally, we would
represent these compounds with the chemical formulas CO
2
and CO, respectively; a convention
introduced by Berzelius, and strongly opposed by Dalton.
The compounds Ferric Chloride and Ferrous Chloride are represented by the chemical
formulas
FeCl
3
and FeCl
2
; where the number of iron atoms is denoted by the symbol Fe (
iron is ferrum in
latin
) and the number of chlorine atoms is denoted by the symbol Cl.
Even at this point in the historical development of chemistry, many questions remaine
d. For
instance, the application of the Law of Multiple Proportions is not unambiguous. How do we
know the order in which to form the ratios? Also, could we interpret the results for the O
xides of
Carbon to mean Carbon Dioxide is really 4 Atoms oxygen to 1 Atom carbon and Carbon
Monoxide is 2 Atoms oxygen to 1 Atom carbon? This interpretation is in fact consistent wit
h the
experimental data and the Law of Multiple Proportions. Thus, the determination of exa
ct
chemical formulas for compounds cannot be done on the basis of the Law of Multiple
Proportions alone. Much more data is required to perform this task. Further, we are now l
eft
with the question of how the atoms bind together to form "molecules?" What accounts for t
he
bonding of these atoms?
Lastly, not all of Dalton's postulates have withstood the test of time. Although his theor
y is
correct in its broad outlines, and is based directly on solid experimental data, sever
al of his
postulates have to be modified in order to conform with modern experimental results. We
will
now turn to an examination of those results.
Questions
1. When a match burns, its mass decreases. Is this a violation of the Law of Conserva
tion of
Mass? Explain.
2. An 8.4g sample of sodium bicarbonate is added to a solution of acetic acid weighing 20.0g
.
The two substances react, releasing carbon dioxide to the atmosphere. After re
action, the
contents of the reaction vessel weigh 24.0g. What is the mass of the carbon dioxide give
n
off during the reaction?
3. Is the Law of Conservation of Mass obeyed in the following experiment:
10.00g of zinc dust is mixed with 2.00g of powdered sulfur and the mixture is heated
carefully. The result is 6.08g of white zinc sulfide and 5.92g of unreacted zinc.
Also, identify the limiting reagent.
4. Is the Law of Conservation of Mass obeyed in the following experiment:
10.00g of calcium carbonate is dissolved in 100.0 mL of hydrochloric acid solution
which has density of 1.148 g/mL. The products are 120.40g of solution and 2.22 L of
carbon dioxide gas, which has a density of 1.9769 g/L.
5. When heated directly, Phosphorus reacts completely with Selenium as follows:
Phosphorus + Selenium Compound #1
(1.00g) (3.82g) (4.82g)
When heated under carbon dioxide and nitrogen, Phosphorus reacts completely with
Selenium as follows:
Phosphorus + Selenium Compound #2
(1.00g) (6.37g) (7.37g)
Determine the elemental composition, percentage by mass, of Compound #1 and
Compound #2.
6. For each experiment, determine the elemental composition, percentage by ma
ss, of the
compound Sodium Chloride.
Expt. 1
1.00g of Sodium metal was allowed to completely react with 10.00g of Chlorine gas.
The Sodium was completely consumed and 2.54g of sodium chloride was produced.
Expt. 2
In a second experiment, 1.00g of Chlorine was allowed to react with 10.00g of
Sodium. The Chlorine was consumed completely and 1.65g of sodium chloride was
produced.
Are the results consistent with the Law of Definite Proportions?
7. Elemental Magnesium reacts with elemental Oxygen to form magnesium ox
ide.
Magnesium oxide has a composition of 60.32% Mg and 39.68% O. How many
grams of Oxygen are required to react completely with 5.00g of Magnesium?
Magnesium + Oxygen Magnesium oxide
8. Hydrogen forms two different Oxides; water and hydrogen peroxide. The re
lative amounts
of hydrogen and oxygen for these two compounds are:
Water Hydrogen Peroxide
mass Hydrogen 1.00g 1.00g
mass Oxygen 7.94g 15.87g
Form the following ratio:
(mass O in Hyd. Per. / mass H) / (mass O in Water / mass H)
Is the result consistent with the Law of Multiple Proportions? (Challenge que
stion: If you
know the chemical formula of water is H
2
O, what is the chemical formula of Hydrogen
Peroxide?)
9. Mercury forms two different Oxides; Mercurous Oxide and Mercuric Oxide
. The relative
amounts of mercury and oxygen in these compounds are:
Mercurous Oxide Mercuric Oxide
mass Mercury 1.00g 1.00g
mass Oxygen 0.0395g 0.0799g
Form the following ratio:
(mass O in Mercuric Ox. / mass Hg) / (mass O in Mercurous Ox. / mass Hg)
Is the result consistent with the Law of Multiple Proportions?
10. Gold forms two different compounds with chlorine:
Aurous chloride
Auric chloride
84.76% Au 64.94% Au
15.24% Cl 35.06% Cl
a) Calculate the mass of Chlorine required to react with 1.00g of Gold to form each o
f
these compounds.
b) Form the following ratio:
(mass Cl in Auric Chl. / mass Au) / (mass Cl in Aurous Chl. / mass Au)
Is the result consistent with the Law of Multiple Proportions?
11. Use the data of Problem #5 to form the following ratio:
(mass Se in Cmpd. #2 / mass P) / (mass Se in Cmpd. #1 / mass P)
Is the result consistent with the Law of Multiple Proportions?

1
FUNDAMENTAL LAWS OF CHEMISTRY
Lavoisier’s Fundamental Laws of Chemistry
- Father of Modern Chemistry
- Late 18
th
century French aristocrat
- Guillotined during the French Revolution.
1.
Law of Mass Conservation
- In any chemical processes, ma
tter cannot be created or destroyed.
2.
Law of Definite Composition
- A chemical compound always has the same mass composition regardless of its
source.
Dalton’s Atomic Theory
- Early 19
th
century British scientist
1. All matter is made of
indivisible atoms.
2.
Elements
are made of one type of atom.
- All atoms have the same chemi
cal and physical properties (mostly).
3. Compounds are made of at
oms in fixed proportions.
- Can’t use ½ of an atom to make a compound.
- Also stated as
Law of Multiple Proportions
.
4. Atoms change arrangement in a
chemical reaction, not identity.

Law of Multiple Proportions

When two elements combine to form two or


more compounds, the ratio formed from
each compound’s mass ratio al
ways yields a fraction.
- In other words, elements cannot combine together with random compositions.
The number of atoms of each
element in a compound must be a whole number.
2
Example: Consider two compounds of sulfur and oxygen.
Compound A has a mass composition of
49.9% oxygen and 50.1% sulfur.
Compound B has a mass composition of
59.9% oxygen and 40.1% sulfur.
The oxygen to sulfur ratio for compound A is
49.9
0.9960
50.1
=
The oxygen to sulfur ratio for compound B is
59.9
1.494
40.1
=
The law of multiple proportions says that a ratio of these ratios must yield a simple
fraction.
0.9960 2
0.6667
1.494 3
=
=
Compound A has two-thirds the oxygen that co
mpound B has. Modern analysis yields
that compound A = SO
2
and compound B = SO
3
.

Basic concepts and laws of chemistry

LAW OF MASS CONSERVATION


(M.V. Lomonosov, 1748, A. Lavoisier 1789)

The mass of the substances entering into a reaction equal the mass of the substances formed
as a result of the reaction.

Atomic-molecular concept explains this law by following manner: as a result of chemical


reactions atoms do not appear and do not disappear, but occurs their rearrangement (i.e.
chemical conversion-process of bond breakup between atoms with another bond formation,
as a result of such conversation the molecules of source substances transform into the
molecules of products of reaction). As far as a number of atoms before and after reaction
stays unchangeable their general mass also must not change. At term «mass» has understood
a value-characterizing amount of matter.

At the beginning of 20 century a formulation of mass conversation law was revising in


connection with the appearance of relativity theory (A. Einstein, 1905), according to which
the mass of substance depends on its velocities, and consequently characterizes not only
matter amount, as well as its motion. An Energy E, obtained by substance, is connected
with increasing its mass m by the correlation E = m * c2, where c is a light velocity. This
correlation is not used in chemical reactions, since 1kJ of energy is corresponding ~ 10-11g
mass changing and practically cannot be measured.

In nucleus reactions, where E greater in 106 times than in chemical reactions, m should
take into account.

Originating from the mass conservation law equations of chemical reactions is possible to
form with the following calculations. It is a basis of quantitative chemical analysis.
Arranging of chemical equations

Include three stages:

1. Record formulas of substances: entered in the reaction (on the left) and products of
reaction (on the right), having connected them on the sense by signs «+», «»:

HgO  Hg + O2

2. Selection the coefficients for each substance so that amount of atoms of each element in
left and right part of equation will be equally:

2HgO  2Hg + O2

3. Checking a number of atoms of each element in left and right parts of equation.

Calculations on chemical equations

Calculations on chemical equations (stoichiometric calculations) are based on the mass


conservation law of substances. In real chemical processes because of incomplete running
chemical reactions and losses a products mass usually less theoretically calculated.

Yield of reaction () is a ratio of real product mass (mr) to theoretically possible (mt),
expressed in shares of units or percent.

If in conditions of problems a yield of reactions products does not specified, its take in
calculations as 100% (quantitative output).

mr
= ––– * 100%
mt
example 1

Calculated the mass of copper formed when reduction 8 g copper oxide by hydrogen. The
yield of reaction – 82% from theoretical.

solution

CuO + H2  Cu + H2O

1. Calculate a theoretical yield of copper on the equation of reaction: 80 g (1 g-mol) CuO


when reducing can form 64 g (1 g-mol) Cu. 8 g CuO – X g Cu.

8 * 64

X = –––– = 6.4 g

80

2. Define how much grams of copper will be formed at 82% yield of product

6.4 g –– 100% 100% yield (theoretical)


X g –– 82%

6.4 * 82

X = –––––– = 5.25 g

100

example 2

Calculate the yield of reaction of tungsten preparation by aluminizing, if from 33.14 g of ore
concentrate, containing WO3 and non-reduce admixtures (mass share of admixtures 0.3),
were obtained 12.72 g of metal.
solution

1. Define the WO3 mass (g) in 33.14 g of ore concentrate.

(WO3) = 1.0 – 0.3 = 0.7

m(WO3) = (WO3) * more = 0.7 * 33.14 = 23.2 g

2. Define the theoretical yield of tungsten as a result of reduction 23.2 g by aluminum


powder.

WO3 + 2Al  Al2 + O3 + W

When reducing 232 g (1g-mol) WO3 form 187 g (1g-mol) W, but at 23.2 g WO3 – X g W

23.2 * 187

X = ————— = 18.7 g W

232

3. Calculate the practical yield of tungsten

18.7 g W –– 100%
12.72 g W –– Y%

12.72 * 100

Y = ––––––––– = 68 %

18.7
example 3

How much grams of barium sulphate will be formed at pouring together the solutions
containing 20.8 g of barium chloride and 18.0 g of sodium sulphate?

solution

BaCl2 + Na2SO4  BaSO4 + 2NaCl

Calculation of product amount carries on the source substance, which is taken in the deficit.

a) Beforehand define which substance stand in the deficit.

Mark the amount of Na2SO4 – X

208 g (1 g-mol) BaCl2 react with 132 g (1 g-mol) Na2SO4

20.8 g with X g

20.8 * 132

X = ————— = 13.2 g Na2SO4

208

We found, that on the reaction with 20.8 g BaCl2 will be spend 13.2 g Na2SO4, but we
have 18.0 g. Thus, sodium sulphate in the reaction is taken in the excess and further
calculation is necessary to carry on the BaCl2, which is taken in deficit.

b) Define quantity of BaSO4 precipitate. 208 g (1 g-mol) BaCl2 form 233 g BaSO4.

20.8 g –– Y g.

233 * 20.8
Y = ————— = 23.3 g
208
Law of constant composition
For the first time has formulated by G. Prust (1808)

"All individual chemical substances have constant quality and quantity composition and
definite chemical structure and does not depend on how this substance was prepared."

From the law of constant composition follows that at complex substance formation the
elements combine with each other in definite mass proportions.

example

CuS- copper sulphide. m (Cu) : m (S) = Ar (Cu) : Ar (S) = 64 : 32 = 2 : 1

To get copper sulphide (CuS) it is necessary to mix up the powders of copper and sulphur in
mass relations 2:1.

If taken amounts of source substances do not correspond their correlation in the chemical
formula of compound one of them stay in the excess.

For instance, if take 3 g. copper and 1 g. sulphur than after the reaction 1 g. copper, which did
not enter in the chemical reaction will stay.

Substances with non-molecular structure do not possess strictly constant composition. Their
composition depends on conditions of preparation.

The mass share of element (e) shows what part forms the mass of given element from the
whole mass of substance: where n – a number of atoms; Ar(e) – relative atomic mass of
element; Mr – relative molecular mass of substance.

n * Ar(e)
(e) = ———
Mr

Knowing the quantitative element composition of substance its simplest molecular formula is
possible to determine:

1. Mark formula of compounds Ax By Cz.

2. Calculate an attitude X: Y: Z through the mass shares of elements:


х * Ar(А) y * Ar(B) z * Ar(C)
(A) = ————— (B) = ————— (C) = —————
Mr(AxByCz) Mr(AxByCz) Mr(AxByCz)

(A) * Mr (B) * Mr (C) * Mr


X = ————— Y = ————— Z = —————

Ar(А) Ar(B) Ar(C)

(A) (B) (C)


x : y : z = —— : —— : ——

Ar(А) Ar(B) Ar(C)

3. Obtained numerals divide on the least for getting total numbers.

4. Write a formula of compound.

Law of multiple proportions


(D. Dalton, 1803)

If two elements form several chemical compounds with each other, then the masses of one of
the elements corresponding to the same mass of the other element in these compounds are in
a simple integral proportion.

N2O N2O3 NO2(N2O4) N2O5

A number of oxygen atoms in molecules of such compounds corresponding to the two


nitrogen atoms are in a proportion 1:3:4:5.
Law of combining volumes
(Gay-Lussac, 1808)

"When gases react, the volumes consumed and produced, measured at the same temperature
and pressure, are in ratios of small whole numbers".

Consequence. Stoichiometric coefficients in equations of chemical reactions for molecules of


gaseous substances shows in which volume combinations gaseous substances are got or react.

examples

a)

2CO + O2  2CO2

In the time of oxidizing of two volumes of carbon (II) oxide by one volume of oxygen forms
2 volume of carbon (IV) oxide, i.e. the volume of source reaction mixture decrease on 1
volume.

b) In the time of synthesis of ammonia from elements:

N2 + 3H2  2NH3

One volume of nitrogen is reacting with three volumes of hydrogen: 2 volumes of ammonia
are forming – the volume of source reaction mixture will be decreased in 2 times.

Avogadro law
(1811)

Equal volumes of all gases at the same conditions (temperature, pressure) contain the same
number of molecules.
This law truth for gaseous substances only.

Consequences:

1. On mole of any substance in the gaseous state occupies the same volume at the same
temperature and pressure.

2. One mole of any gas in standard conditions (0°C = 273K, 1 atm = 101.3 kPa) occupies a
volume of 22.4 litres.

example 1

What volume of hydrogen at s.t.p. would be evolved at dissolution 4.8 g magnesium in


excess of hydrochloric acid?

solution

Mg + 2HCl  MgCl2 + H2

At dissolution of 24 g (1 g-mol) magnesium in HCl –– 22.4 l (1 g-mol) of hydrogen is


evaluated; at dissolution of 4.8 g of magnesium –– X l of hydrogen.

4.8 * 22.4
X = ———— = 4.48 l of hydrogen
24

example 2

3.17 g of chlorine is borrowing volume, which equal 1 l (at s.t.p.). Calculate the molecular
mass of chlorine.

solution

Find mass of 22.4 l chlorine.

1 l –– 3.17 g of hydrogen
22.4 l –– X g of hydrogen

X = 3.17 * 22.4 = 71 g

General gas law

General gas law is association of three independent private gas laws: Gay-Lussac’s, Charle’s,
Boyl’s- Mariott’s, equation which possible write like this:

P1V1 P2V2
—— = ——
T1 T2

Conversely, from general gas law under P= const. (P1=P2), possible to get:

V1 V2
— = —
T1 T2

(Gay-Lussac’s law)

On the T=const. (T1=T2): P1V1= P2V2 (Boyl’s-Mariott’s law).

On the V=const.

P1 P2
— = —
T1 T2

(Charle’s law).
Clapeyron’s - Mendeleyev’s equation

If write general gas law for any mass of any gas than would be Clapeyron’s - Mendeleyev’s

equation:

m
PV = — RT
M

where, m - gas mass; M - molecular mass; p - pressure; V - volume; T - absolute temperature


(K); R - molar gas constant (8.314 J/(mol * K) or 0.082 l atm/(mol * K)).

For given mass of concrete gas the ratio m/M is a constant, therefore general gas law is
obtained from Clapeyron’s - Mendeleyev’s equation.

example

What volume would be reserved by carbon (II) oxide with mass 84 g at temperature 17°C and
pressure 250 kPa?

solution

Quantity g-mol of CO is:

m(CO) 84
(CO) = —— = — = 3 g-mol
M(CO) 28

CO volume at s.t.p is 3 * 22.4 l = 67.2 l

From general gas law of Boyl’s-Mariott’s and Gay-Lussac’s:


P * V P0 * V0
—— = ——
T T2

follows:

P0 * T * V0 101.3 * (273 + 17) * 67.2


V(CO) = ————— = ——————————— = 28.93 l
P * T0 250 * 273

Relative density of gases shows in how many times 1 mol of one gas more heavy (or easier)
than 1 mol of another.

(B) M(B)
DA(B) = —— = ——
(A) M(A)

The average molecular mass of gases mixture is peer to a common mass of mixture bisected
on a total number of moles:

m1 +.... + mn M1 * V1 + .... Mn * Vn
Mav = —————— = —————————
1 +.... + n 1 +.... + n

example 1

The density of certain gaseous substance on hydrogen is 17. Calculate its density on air
(Mav=29).

solution

Msub Мsub
DH2 = —— = ——
M H2 2

Мsub = 2DH2 = 34
Msub 34
Dair = ——— = —— = 1.17
Mair av. 29

example 2

Define the density of nitrogen, argon, and carbon (II) oxide mixture on air, if the mass parts
of components are 15, 50 and 35% respectively.

solution

Mmix Мmix
Dmix (on air) = —— = ——
Mair 29

15 * 28 + 50 * 40 + 35 * 44 420 + 2000 + 1540


Mmix = ——————————— = ———————— = 39.6
100 100

Mmix 39.6
Dmix (on air) = —— = —— = 1.37
29 29

Planetary model of atom structure


(E. Rutherford, 1911)

1. Atoms of chemical elements have a complex internal structure.

2. In the center of atom locate positive charged nucleus, occupying insignificant part of
spaces inside atom.

3. The whole positive charge and almost the whole mass of atom concentrated in atom
nucleus (the mass of electron is 1/1823 a.e.m.)

4. Electrons are moved around the nucleus on the closed orbital. Their number is a charge
of a nucleus. Therefore, atom as a whole is electrically neutral.
Nucleus of atom

Atomic nuclei consist of protons and neutrons (general title - nucleons). The number of
protons (Z) in atomic nuclei is strictly defined and equal to the serial number of element in
the Periodic system. The number of neutrons in the atomic nuclei of one and the same
element can be different - A-Z (where A - relative atomic mass of element; Z- serial number).

The number of protons defines nucleus charge of atom.

Nucleus mass is defined by the sum of protons and neutrons.

Isotopes

Isotopes- variety of atoms of certain chemical elements, having an identical atomic number,
but different mass numbers. Isotopes have nucleuses with an identical number of protons and
different number of neutrons.

Isotopes have an identical structure of electronic shell and occupy one and the same place in
the Periodic table of chemical elements.

example

Native thallium (atomic number 81, atomic mass 204.383) consist of two isotopes:

Thallium-203

203 1 1
Tl (81 p1; 122 n0) - 29,5%
81

Thallium-205

205 1 1
Tl (81 p ; 124 n ) - 70,5%
81 1 0
Average atomic mass of thallium is:

0.295 * 203 + 0.705 * 205


Aav.(Tl) = ———————————— = 204.383
2

Hydrogen isotopes have special symbols and names:

1 2 3
H- protium; D - deuterium; T- tritium.
1 1 1

Chemical properties of isotopes of one element are equal. Isotopes having an identical mass
numbers, but different nucleus charge are called isobars.

40 40 40 112 112
( Ar, K and Ca; Cd and Sn).
18 19 20 48 50

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