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:
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:
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.
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:
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.
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:
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:
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.
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 %
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:
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.
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.
The mass of the substances entering into a reaction equal the mass of the substances formed
as a result of the reaction.
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
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.
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
8 * 64
X = –––– = 6.4 g
80
2. Define how much grams of copper will be formed at 82% yield of product
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
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
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
Calculation of product amount carries on the source substance, which is taken in the deficit.
20.8 g with X g
20.8 * 132
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
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:
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.
"When gases react, the volumes consumed and produced, measured at the same temperature
and pressure, are in ratios of small whole numbers".
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.
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 = 273K, 1 atm = 101.3 kPa) occupies a
volume of 22.4 litres.
example 1
solution
Mg + 2HCl MgCl2 + H2
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
1 l –– 3.17 g of hydrogen
22.4 l –– X g of hydrogen
X = 3.17 * 22.4 = 71 g
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 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
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
m(CO) 84
(CO) = —— = — = 3 g-mol
M(CO) 28
follows:
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
Mmix 39.6
Dmix (on air) = —— = —— = 1.37
29 29
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).
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:
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