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PHYSICAL CHEMISTRY By--
P
.K.SINHA
Contact atpknoida1@gmail.com
Moles Concept,
What is a Mole?
Since atoms and molecules are so tiny, it is convenient to talk about a large number of them at a time.The chemical counting unit is known as the mole. A mole is defined as the amount of substance thatcontains as many elementary entities (atoms, molecules, or other particles) as there are atoms in exactly12 g of the
612
C 
isotope. It has been found experimentally that
1 mole of particles=6.022 x 10
23
particles
This value is known as Avogadro
’
s number. Just like 1
dozen of anything always contains 12 items, 1 mole of anything always contains 6.022 x 1023items.
Atomic Mass and Molar Mass
Isotopic masses cannot be obtained by summing the masses of the elementary particles (neutrons,protons, and electrons) from which the isotope is formed. This process would give masses slightly toolarge, since mass is lost when the neutrons and protons come together to form the nucleus.Atomic masses (also called atomic weights) are thus assigned relative to the mass of a particular carbonisotope,
612
C 
, which is assigned the mass of 12 amu exactly. Likewise 1 mole of
612
C 
has a mass ofexactly 12 g. Atomic masses and molar masses of other isotopes are calculated based on their massrelative to that of Carbon-12.Masses of
“
average
”
atoms are found by summing isotopic masses, weighting each isotopic mass by its
abundance . Thus one
“
ave
rage
”
C atom
has a mass of 12.01 amu, and the mass of 1 mole of
“
average
”
 
carbon atoms has a mass of 12.01 g. These average masses are what are given on the periodic chart.
Molecular Masses and Compound Masses
Molecular masses are found by summing atomic masses . They are often called molecular weights. Thusthe mass of 1 mole of water, H2O, would be 2 x (molar mass of H) plus 1x (molar mass of O) or [(2 x1.008 g) + (1 x 16.00 g)] = 18.02 g.Ionic compounds such as NaCl do not contain molecules. Their formulas give the relative numbers ofeach kind of atom in the sample. What we mean by the molar mass (or the molecular weight) of an ioniccompound is really the formula weight. The formula weight is the sum of the atomic masses in theformula
.
Percent Composition of Compounds
The percent composition by mass is the percent by mass of each element in a compound. If there are nmoles of an element per mole of compound, the percent by mass of the element is calculated using theequation,
% Composition of Element=
n
 
molar mass of elementmolar mass of compound
  
 
100%
 
The sum of the % compositions of all elements in a compound is 100%.
Exercises
1. The atomic mass scale gives masses in atomic mass units (amu) relative to the mass of carbon-12.(a) What is the mass of one
12
C atom in atomic mass units (amu)?(b) What is the mass of an average C atom in atomic mass units (amu)?(c) What is the mass of an average Cl atom in amu?(d) What is the mass of an average Br atom in amu?2. The molar mass scale gives masses in grams (g) relative to the mass of
12
C.(a) What is the mass in grams of 1 mole (mol) of
12
C?(b) What is the mass in grams of 1 mole (mol) of carbon?(c) What is the mass in grams of 1 mole (mol) of Cl?(d) What is the mass in grams of 1 mole (mol) of Na?3. How many
12
C atoms are present in a mole of
12
C ?4. Cinnamic alcohol is used mainly in perfumery, particularly in soaps and cosmetics. Its molecularformula is C
9
H
10
O.(a) Calculate the percent composition by mass of C, H, and O in cinnamic alcohol.(b) How many molecules of cinnamic alcohol are contained in a sample of mass 0.469 g?
1
 
PHYSICAL CHEMISTRY By--
P
.K.SINHA
Contact atpknoida1@gmail.com
Answers:
1. (a) 12 amu exactly; (b) 12.01 amu; (c) 35.45 amu; (d) 79.90 amu.2. (a) 12 g exactly; (b) 12.01 g; (c) 35.45 g; (d) 22.99 g.3. 6.022 x 10
23
atoms of
12
C.4. (a) 80.56% C; 7.51% H; 11.93% O; (b) 2.11 x 10
21
molecules of C
9
H
10
O.
Empirical and Molecular Formulas
The empirical formula of a compound gives the simplest whole number ratio of differenttypes of atoms in the compound.
All salt formulas are empirical formulas. On the other hand, themolecular formula of a compound may or may not be the same as its empirical formula. For example,the molecular formula of butane is C
4
H
10
while its empirical formula is C
2
H
5
.
The molecular formulagives the true number of each kind of atom in a molecule.
 
Empirical formulas may be easily determined from experimental data.
 
Usually you must first determine how many grams of each type of atom are in the compound. If percent composition data is given, assume that you have 100.0 g of the compound; then the number of grams of each element is equal to the percentage for that element.
 
The next task is convert the grams of each element to moles of the element. Be sure to keep at leastthree significant figures in your answers.
 
The final step is to write the molar amounts of each element as subscripts in the formula. Thendivide all molar subscripts by the smallest value in the set. At this point, the subscripts may all be veryclose to whole numbers; if so, you are finished. If one (or more) of the subscripts is not close to awhole number, multiply all molar subscripts by the simple factor which makes all subscripts wholenumbers.
 
Once the empirical formula is determined, the molecular formula is easily found if the molar mass(molecular weight) of the molecule is also known. You first calculate the molar mass of the empiricalformula. Then you divide the molar mass of the molecule by the molar mass of the empirical formula.The division should give a simple whole number. That number is the factor by which all subscripts inthe empirical formula must be multiplied to obtain the molecular formula.
Exercises
1. The molecular formula of the antifreeze ethylene glycol is C
2
H
6
O
2
. What is the empirical formula?2. A well-known reagent in analytical chemistry, dimethylglyoxime, has the empirical formula C
2
H
4
NO.If its molar mass is 116.1 g/mol, what is the molecular formula of the compound?3. Nitrogen and oxygen form an extensive series of oxides with the general formula N
x
O
y
. One of themis a blue solid that comes apart, reversibly, in the gas phase. It contains 36.84% N. What is the empiricalformula of this oxide?4. A sample of indium chloride weighing 0.5000 g is found to contain 0.2404 g of chlorine What is theempirical formula of the indium compound?
Answers:
1. CH3O2. Molar mass of empirical formula is 58.06 g/mol. Thus molecular formula is C4H8N2O2.3. The ratios are
N
1.00
O
1.50
. Since 1.50 is not close to a whole number, we multiply both subscripts by2. The empirical formula is thus N2O3. (The name is dinitrogen trioxide.)4. InCl3.
 
Chemical Stoichiometry Problems
 
Calculating the yield of a chemical reaction is a process at the heart of chemistry. While there are manyways a problem can be phrased, in all cases the stoichiometric coefficientsin the balanced reaction areused to determine the mole ratios between reactants and products. Thus the first step is usuallycalculating the moles of each species available. If an amount is given in grams, the molar mass is used
2
 
PHYSICAL CHEMISTRY By--
P
.K.SINHA
Contact atpknoida1@gmail.com
as a conversion factor to change grams to moles.
Limiting Reagent Problems
In some problems, amounts of more than one species are given. In that case your first task is todetermine which species is the limiting reagent. Just as you can make only 1 bicycle from 2 wheels and4 handlebars (with 3 handlebars left over), and only 2 bicycles from 8 wheels and 2 handlebars (with 4wheels left over), in chemical reactions some species are limiting while others may be present in excess.In the case of a bicycle, we need
2 wheels1 handlebar
  
. We obtain analogous information about the relativeamounts of species that react from the stoichiometric coefficients in a balanced chemical equation. Forexample, in Exercise (2) below the equation CO(g) + 2 H
2
(g)
CH
3
OH (l)tells us we need
2 mol H
2
1 mol CO
  
. If we have more than 2 moles of H
2
for each mole of CO, CO will be thelimiting reagent and the excess H
2
will not react. Conversely, if we have more than 1 mole of CO forevery 2 moles of H
2
, H
2
will be the limiting reagent and the excess CO(g) will be left over. In each case,the yield of CH
3
OH is determined by the moles of limiting reagent available.
 
Calculating the Theoretical Yield
The theoretical (maximum possible) yield is based on the amount of limiting reagent available. The yieldis calculated in steps:
•
Calculate moles of all reactants available. If amounts are given in grams, convert grams to moles usingthe molar mass of each reactant as your conversion factor:
1 mole reactant# g reactant
  
.
•
NOTE
: Skip this step if you have already identified the limiting reagent. To determine which reagent islimiting, use the mole ratio obtained from the balanced equation for the reaction to find the moles ofreactant B needed to react with the available moles of reactant A. If the moles of B available are lessthan the moles of B needed, reactant B is the limiting reagent and reactant A is in excess. Conversely, ifthe moles of B available are more than the moles of B needed, A is the limiting reagent and B is inexcess.
•
Calculate the molesof product based on the moles of limiting reagent available; use the stoichiometricratio of
# moles product# moles limiting reagent
  
as the conversion factor.
•
If you are asked for the yield in grams, convert the yield in moles to a yield in grams using the molarmass as your conversion factor:
# g product1 mole product
  
 
Percent Yield
Most reactions do not go to completion, and so the actual yield is less than the percent yield.The percent yield is calculated as
Percent yield=actual yieldtheoretical yield
  
100%
 
Exercises:
1. Ammonia is produced by the reaction3 H
2
(g) + N
2
(g)

2 NH
3
(g)(a) If N
2
(g) is present in excess and 55.6 g of H
2
(g) reacts, what is the theoretical yield of NH
3
(g)?(b) What is the percent yield if the actual yield of the reaction is 159 g of NH
3
(g)?Answers: 1(a) 313 g NH
3
(g); (b) 50.8% yield.2. Methyl alcohol (wood alcohol), CH
3
OH, is produced via the reactionCO(g) + 2 H
2
(g)
CH
3
OH (l)Answers: 2(a) CO is the limiting reagent; (b) 8.52 g CH
3
OH; (c) 0.13 g H
2
; (d) 88.3%
3
of 00

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