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Chapter-3 - Mass Relationships in Chemical Reactions
Chapter-3 - Mass Relationships in Chemical Reactions
MASS RELATIONSHIPS IN
CHEMICAL REACTIONS
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In this chapter, we’ll begin learning about how to describe chemical reactions, starting with
a look at the conventions for writing chemical equations and at the mass relationships
between reactants and products. Because most chemical reactions are carried out using
solutions rather than pure substances, we’ll also discuss units for describing the
concentration of a substance in solution. Finally, we’ll see how chemical formulas are
determined and how molecular masses are measured.
2H2 + O2 → 2H2O
4 H and 2 O atoms 4 H and 2 O atoms
on this side on this side
We must write hydrogen and oxygen as H 2 and O2 in chemical equations since they exist as
covalent diatomic molecules. Now look at the atoms on each side of the reaction arrow. The
numbers and kinds of atoms on both sides of the reaction arrow are the same. This is called
a balanced chemical equation. Balancing of chemical equations is carried out as a
consequence of the mass conservation law. A chemical equation is balanced in order to find
out how many formula units of each different substance take part in the reaction. A formula
unit implies one unit—whether atom, ion, or molecule—corresponding to a given formula.
For example one formula unit of NaCl is one ion and one ion, one formula unit of MgBr 2 is
one ion and two ions, and one formula unit of H2O is one H2O molecule.
Complicated equations generally need to be balanced using a systematic method, such as
we’ll discuss in the next chapter, but simpler equations can often be balanced using a
mixture of common sense and trial-and-error:
1. Write the unbalanced equation using the correct chemical formula for each reactant and
product. For example, the chemical equation for combustion of methane (CH 4) with
oxygen to yield carbon dioxide and water can be written as:
2. Find suitable coefficients—the numbers placed before formulas to indicate how many
formula units of each substance are required to balance the equation. Only these
coefficients can be changed when balancing an equation; the formulas themselves can’t
be changed. The above equation can be balanced by adding a coefficient of 2 to both O 2
and H2O. By doing so, we now have 1 carbon atom, 4 hydrogen atoms, and 4 oxygen
atoms on both sides of the equation as shown below.
2
3. Reduce the coefficients to their smallest whole-number values, if necessary, by dividing
them all by a common divisor.
4. Check your answer by making sure that the numbers and kinds of atoms are the same
on both sides of the equation.
Balance the chemical equation for the reaction of table sugar (sucrose, C 12H22O11) with
potassium chlorate (KClO3), a major ingredient in ordinary safety matches as a source of
oxygen in combustion reactions to yield potassium chloride, carbon dioxide and water.
SOLUTION:
Step1. The unbalanced equation with the correct formulas for all substances was written
first.
Step2. Coefficients were found to balance the equation by starting with the most complex
substance (sucrose) and considering one element at a time. Since there are 12 C atoms on
the left and only 1 on the right, a coefficient of 12 was added to CO 2 in order to balance
carbon atoms on the right.
Since there are 22 H atoms on the left and only 2 on the right, we can balance for hydrogen
by adding a coefficient of 11 to H2O on the right.
There are now 35 O atoms on the right but only 14 on the left (11 in sucrose and 3 in KClO 3).
Thus, 21 oxygen atoms must be added on the left. This was done by giving a coefficient of 8
for KClO3 on the left without disturbing C and H.
Potassium and chlorine can both be balanced by adding a coefficient of 8 to KCl on the right.
Step3 and 4. The coefficients in the balanced equation are already reduced to their smallest
whole-number values and a check shows that the numbers and kinds of atoms are same on
both sides of the equation.
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PROBLEM 3.1 Balance the following equations:
On the macroscopic level, formulas and equations represent the large-scale behaviors of
atoms and molecules that give rise to visible properties. In other words, the symbols H 2, O2,
and H2O represent not just single molecules but vast numbers of molecules that together
have a set of measurable physical properties. A single isolated H2O molecule is neither solid
nor liquid nor gas, but a huge collection of H 2O molecules appears to us as a colorless liquid
that freezes at 0 °C and boils at 100 °C. Clearly, it’s this macroscopic behavior we deal with
in the laboratory when we weigh specific amounts of reactants, place them in a flask, and
observe visible changes. In the same way, a single atom of copper is neither solid, liquid, nor
gas, does not conduct electricity, and has no color on a microscopic level. On a macroscopic
level, however, a large collection of copper atoms appears to us as a shiny, reddish-brown
metal that can be drawn into electrical wires or made into coins. What does a chemical
formula or equation mean? It means different things depending on the context. The symbol
H2O can mean either one tiny, invisible molecule or a vast collection of molecules large
enough to swim in.
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3.3 Chemical Arithmatic: Stoichiometry
In order to find the amount of reactants required to carry out an experiment, we have to
proceed as follows:
The physical state of reactants and products in chemical equations are indicated by writing
(g) for gas, (l) for liquid, (s ) for solid, and (aq) for aqueous solutions after their symbols or
formulae.Molar mass of C2H4 = 28.0 g/mol. That means 28g of C2H4 is 1 mole of C2H4. So 15 g
of C2H4 is 15/28 = 0.536 moles of C 2H4. We know from the balanced equation that 1mole of
ethylene reacts with one mole of HCl. So 0.536 mole of ethylene react with 0.536 mole of
HCl. Again molar mass of HCl is 36.5 g/mol. It means 1 mole of HCl weighs 36.5 grams. 0.536
moles of HCl weigh 36.5×0.536 = 19.6 g HCl. Therefore, 19.6 g of HCl is needed to react with
15.0 g of ethylene.
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PROBLEM 3.3 Aspirin is prepared by reaction of salicylic acid (C 7H6O3) with acetic anhydride
(C4H6O3) according to the following equation:
acid anhydride
(a) How many grams of acetic anhydride are needed to react with 4.50 g of salicylic acid?
Methyl tert-butyl ether (MTBE, C5H12O), a gasoline additive now being phased out in many
places because of health concerns, can be made by reaction of isobutylene (C 4H8) with
methanol (CH4O). What is the percent yield of the reaction if 32.8 g of methyl tertbutyl ether
is obtained from reaction of 26.3 g of isobutylene with sufficient methanol?
ether (MTBE)
SOLUTION
Isobutylene (C4H8): Molec. mass = (4 × 12.0 amu) + (8 × 1.0 amu) = 56.0 amu
MTBE, (C5H12O): Molec. mass = (5 × 12.0 amu) + (12 × 1.0 amu) + 16.0 amu = = 88.0 amu
To calculate the amount of MTBE that could theoretically be produced from 26.3 g of
isobutylene, we first have to find the number of moles of reactant, using molar mass as the
conversion factor:
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56.0 g isobutylene = 1mol isobutylene
According to the balanced equation, 1 mol of product is produced per mol of reactant, so
we know that 0.470 mol of isobutylene can theoretically yield 0.470 mol of MTBE.
Whenever the ratios of reactant molecules used in an experiment are different from
those given by the coefficients of the balanced equation, a surplus of one reactant is left
over after the reaction is finished. Thus, the extent to which a chemical reaction takes place
depends on the reactant that is present in limiting amount—the limiting reactant. The other
reactant is said to be the excess reactant.
Worked Example 3.5 shows how to tell whether a limiting amount of one reactant is present
and how to calculate the amounts of the excess reactant consumed and remaining.
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Worked Example 3.5
Cisplatin, an anticancer agent used for the treatment of solid tumors, is prepared by the
reaction of ammonia with potassium tetrachloroplatinate. Assume that 10.0 g of K2PtCl4
and 10.0 g of NH3 are allowed to react
Potassium Cisplatin
Tetrachloro palatinate
(b) How many grams of the excess reactant are consumed, and how many grams remain?
SOLUTION
(a) Finding the molar amounts of reactants always begins by calculating formula masses and
using molar masses as conversion factors:
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(c) The balanced equation shows that 1 mol of cisplatin is formed for each mole of K2PtCl4
consumed. Thus, 0.0241 mol of cisplatin is formed from 0.0241 mol of K2PtCl4. To
determine the mass of cisplatin produced, we must calculate its molarmass and then
carry out a mole-to-gram conversion.
Molec. mass of Pt(NH3)2Cl2 = 195.1 amu + (2 × 17.0 amu) + (2 ×35.5 amu) = 300.1 amu
PROBLEM 3.5 Lithium oxide is used aboard the space shuttle to remove water from the air
supply. If 80.0 kg of water is to be removed and 65 kg of Li2O is available, which reactant is
limiting? How many kilograms of the excess reactant remain?
Molarity can be used as a conversion factor to relate a solution’s volume to the number of
moles of solute. If we know the molarity and volume of a solution, we can calculate the
number of moles of solute. If we know the number of moles of solute and the molarity of
the solution, we can find the solution’s volume by using above relation.
What is the molarity of a solution made by dissolving 2.355 g of sulfuric acid (H2SO4) in
water and diluting to a final volume of 50.0 mL?
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SOLUTION
Molec. mass of H2SO4 = (2 × 1.0 amu) + 32.1 amu + (4 × 16.0 amu) = 98.1 amu
PROBLEM 3.13 How many grams of solute would you use to prepare the following
solutions?
The main thing to remember when diluting a concentrated solution is that the number of
moles of solute is constant; only the volume of the solution is changed by adding more
solvent.
Following relation is used to find the volume of a concentrated solution of known molarity
required for making given volume of dilute solution of known molarity.
Mi × Vi = Mf × Vf
where Mi is the initial molarity, Vi is the initial volume, Mf is the final molarity, and Vf is the
final volume after dilution.
How would you prepare 500.0 mL of 0.2500 M NaOH solution starting from a concentration
of 1.000 M?
SOLUTION
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We know that Mi × Vi = Mf × Vf.
Hence we need 125.0 mL of 1.000 M NaOH solution to prepare 500.0 mL of 0.2500 M NaOH
solution.
PROBLEM 3.7
Sulfuric acid is normally purchased at a concentration of 18.0 M. How would you prepare
250.0Ml of 0.500 M aqueous H2SO4? (Remember to add the acid to water rather than
water to the acid.)
A dilute solution of HCl in water (stomach acid) can be neutralized by reaction with sodium
hydrogen carbonate (NaHCO3), according the following equation.
How many milliliters of 0.125 M NaHCO 3 solution are needed to neutralize 18.0 mL of
0.100M HCl?
SOLUTION
We know from above balanced chemical equation that one mole of NaHCO 3 neutralises one
mole of HCl. So 1.8 ×10-3mol. HCl will be neutralized by 1.8 ×10 -3mol. NaHCO3. 0.125 M
NaHCO3 solution means:
Thus, 14.4 milliliters of 0.125 M NaHCO 3 solution are needed to neutralize 18.0 mL of
0.100M HCl.
PROBLEM 3.8
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What volume of 0.250 M H2SO4 is needed to react with 50.0 mL of 0.100 M NaOH? The
equation is H2SO4 (aq) + 2 NaOH(aq) → Na2SO4(aq) + 2 H2O(l)
3.9 Titration
There are two ways to make a solution of known molarity.
20 mL of HCl solution is titrated and found to react with 48.6 mL 0f 0.100M NaOH. Find out
the molarity of HCl solution.
SOLUTION
We have to find out the concentration of HCl (an acid) solution by reacting it with a base
(NaOH). It is called an acid – base neutralization reaction and the balanced equation for this
reaction is written below.
This reaction will be carried out by titration which is carried out by following steps.
Step – 2: A small amount of indicator, a compound that undergoes a colour change during
the course of reaction is added to this solution. Phenolpthalein can be used as an indicator
in this case because it is colourless in acidic solution and turns red in basic solution.
Step – 3: 0.100M NaOH solution (standard solution) is known) is taken in a calibrated glass
tube called buret and is slowly added to HCl solution. When colour of the solution is just
changed to pink (phenolpthalein turns pink), all the HCl reacted completely and the solution
now has a tiny amount of excess NaOH. This is called end point. Then the volume of
standard solution (NaOH) is measured from burette. In this case it was found to be 48.6 mL.
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1000 mL of the solution contains 0.100 moles of NaOH
48.6 mL of the solution contains (0.100 / 1000) × 48.6 = 0.00486 mol. of NaOH.
According to the balanced equation, the number of moles of HCl is the same as that of
NaOH. So 20 mL of HCl solution contains 0.00486 mol. of HCl
1000mL of HCl contains (0.00486/ 20) × 1000 = (0.004 86 mol HCl )/0.0200 L HCl = 0.243 M
HCl.
PROBLEM 3.9 A 25.0 mL sample of vinegar (dilute acetic acid, CH3CO2H) is titrated and
found to react with 94.7 mL of 0.200 M NaOH. What is the molarity of the acetic acid
solution? The reaction is
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4 to get whole number and the empirical formula of the compound can be
written as C4H9.04 = C4H9.
(v) The molecular formula, which tells the actual numbers of atoms in a
molecule, can either be same as empirical formula or be a simple multiple of
it. To determine the molecular formula, it is necessary to know molecular
mass of the substance. In the present instance, molecular mass of the
compound (octane) is 114.2 amu, which is a simple multiple of the empirical
formula mass (C4H9) 57.1. To find the multiple, molecular mass is divided by
empirical formula mass.
Multiple = molecular mass/ empirical formula mass = 114.2/57.1 = 2.00.
(vi) The subscripts in the empirical formula are multiplied by this multiple to
obtain molecular formula. Thus the molecular formula of the compound
(octane) is C(4×2)H(9×2) = C8H18.
(i) The mole ratio of elements of the compound (aspirin) is to be found out. i.e
C: H: O = 9:8:4.
(ii) The mole ratio is then converted to mass ratio and thus into percentage
composition by carrying out mole to gram conversions. Mass ratio of
elements of aspirin, C: H: O = (12 ×9) : (8×1.01): (4×16) = 108: 8.08: 64.
(iii) Total mass of 1 mole of the substance is calculated. Total mass of 1 mole of
aspirin = 108 + 8.08 + 64 = 180 g.
(iv) Mass ratio of each element is divided by total mass and is multiplied by 100
to get percentage composition.
So % C = 108/180) ×100 = 60.0
% H = 8.08/ 180) ×100 = 4.49
% O = 64/180) × 100 = 35.6
The answer can be checked by confirming that the sum of the mass
percentage is within a rounding error of 100%.
PROBLEM 3.10
What is the empirical formula of the ingredient in Bufferin tablets that has the percentage
composition C 14.25%, O 56.93%, Mg 28.83% by mass?
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One of the most common methods used to determine percentage composition and
empirical formulas, particularly for organic compounds containing carbon and hydrogen is
combustion analysis. In this method, a compound of unknown composition is burned with
oxygen to produce the volatile combustion products CO 2 and H2O, which are separated and
have their amounts determined by an automated instrumebnt. For example, methane (CH 4)
burns according to the balanced equation
After calculating the weights of CO2 and H2O, the number of moles of C and H2 in the
product are calculated. C:H mole ratio of the starting compound is then found out. This
information provides the chemical formula.
As an example of how combustion analysis works, imagine that we have a sample of a pure
substance—say, naphthalene, which is often used for household moth balls. We weigh a
known amount of the sample, burn it in pure oxygen, and then analyze the products. Let’s
say that 0.330 g of naphthalene reacts with O2 and that 1.133 g of CO2 and 0.185 g of H2O
are formed. The first thing to find out is the number of moles of carbon and hydrogen in the
CO2 and H2O products so that we can calculate the number of moles of each element
originally present in the naphthalene sample.
Although it’s not necessary in this instance since naphthalene contains only carbon and
hydrogen, we can make sure that all the mass is accounted for and that no other elements
are present. To do so, we carry out mole-to-gram conversions to find the number of grams
of C and H in the starting sample:
Because the total mass of the C and H in the products (0.3298 g) is the same as the mass of
the starting sample (0.330 g), we know that no other elements are present in naphthalene.
With the relative number of moles of C and H in naphthalene known, divide the larger
number of moles by the smaller number to get the formula C1.26H1.
Then multiply the subscripts by small integers in a trial-and-error procedure until whole
numbers are found to obtain the whole-number formula C5H4:
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Multiply subscripts by 4 : C(1.26*4)H(1*4) = C5.04H4 = C5H4
Elemental analysis provides only an empirical formula. To determine the molecular formula,
it’s also necessary to know the substance’s molecular mass. In the present problem, the
molecular mass of naphthalene is 128.2 amu, or twice the empirical formula mass of C5H4
(64.1 amu). Thus, the molecular formula of naphthalene is C(2×5)H (2×4) = C10H8.
Worked Example 3.17 shows a combustion analysis when the sample contains oxygen in
addition to carbon and hydrogen. Because oxygen yields no combustion products, its
presence in a molecule can’t be directly detected by this method. Rather, the presence of
oxygen must be inferred by subtracting the calculated masses of C and H from the total
mass of the sample.
Caproic acid, the substance responsible for the aroma of goats, dirty socks, and old shoes,
contains carbon, hydrogen, and oxygen. On combustion analysis, a 0.450 g sample of
caproic acid gives 0.418 g of H2O and 1.023 g of CO2. What is the empirical formula of
caproic acid? If the molecular mass of caproic acid is 116.2 amu, what is the molecular
formula?
SOLUTION
Subtracting the masses of C and H from the mass of the starting sample indicates that 0.124
g is unaccounted for: 0.450 g - (0.2791 g + 0.0469 g) = 0.124 g
Because we are told that oxygen is also present in the sample, the “missing” mass must be
due to oxygen, which can’t be detected by combustion. We therefore need to find the
number of moles of oxygen in the sample: Moles of O = 0.124 /16.00 = 0.007 75 mol O
Knowing the relative numbers of moles of all three elements, C, H, and O, we divide the
three numbers of moles by the smallest number (0.007 75 mol of oxygen) to arrive at a C: H:
O ratio of 3:6:1.
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The empirical formula of caproic acid is therefore C3H6O, and the empirical formula mass is
58.1 amu. Because the molecular mass of caproic acid is 116.2, or twice the empirical
formula mass, the molecular formula of caproic acid must be C (2×3)H(2×6)O(2×1) = C6H12O2.
PROBLEM 3.11 Menthol, a flavoring agent obtained from peppermint oil, contains carbon,
hydrogen, and oxygen. On combustion analysis, 1.00 g of menthol yields 1.161 g of H2O and
2.818 g of CO2. What is the empirical formula of menthol?
The radius of deflection of a charged ion (M +) as it passes between the magnet poles
depends on its mass, with lighter ions deflected more strongly than heavier ones. By varying
the strength of the magnetic field, it’s possible to focus ions of different masses through a
slit at the end of the curved pipe and onto a detector assembly. The mass spectrum that
results is plotted as a graph of ion mass versus intensity—that is, as the molecular masses of
the various ions versus the relative number of those ions produced in the instrument.
Although a typical mass spectrum contains ions of many different masses, the heaviest ion is
generally due to the ionized molecule itself, the so-called molecular ion. By measuring the
mass of this molecular ion, the molecular mass of the molecule can be determined. The
naphthalene sample discussed in the previous section, for example, gives rise to an intense
peak at mass 128 amu in its spectrum, consistent with a molecular formula of C10H8.
Modern mass spectrometers are so precise that molecular masses can often be measured to
seven significant figures. A 12C10 1H8 molecule of naphthalene, for example, has a molecular
mass of 128.0626 amu as measured by mass spectrometry.
***
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