Part 1 · Chapter 1

Some Basic Concepts of Chemistry

The grammar of chemistry — matter, measurement, the mole and the balanced equation that every later calculation rests upon

Fundamentals of Chemistry Prof. Mithun Mondal Reading time ≈ 40 min
i What you'll learn
  • How matter is classified into elements, compounds and mixtures.
  • The SI units, the rules of significant figures, and the factor-label method of dimensional analysis.
  • The five laws of chemical combination and how Dalton's atomic theory explains them.
  • The central idea of the mole and the bridge \(n=\dfrac{m}{M}=\dfrac{N}{N_A}=\dfrac{V}{V_m}\).
  • How to find an empirical and molecular formula from percentage composition.
  • How to do stoichiometry, identify the limiting reagent, and express concentration as molarity, molality and mole fraction.
Section 1-1

Matter and Its Classification

Matter is anything that has mass and occupies space. Physically it appears in three common states — solid, liquid and gas — distinguished by how tightly its particles are held and how freely they move. Chemically, the more important question is whether a sample is pure or a mixture.

A pure substance has a fixed composition and a unique set of properties. It is either an element (one kind of atom, e.g. \(\ce{Na}\), \(\ce{O2}\)) or a compound (two or more elements chemically combined in a fixed mass ratio, e.g. \(\ce{H2O}\)). A mixture contains two or more substances in any proportion, separable by physical means; it is homogeneous (uniform throughout, like salt solution) or heterogeneous (non-uniform, like sand in water).

MATTER Mixtures Pure substances Homogeneous air, brine Heterogeneous sand + water Elements Na, O₂, Fe Compounds H₂O, NaCl mixtures → physical methods · compounds → chemical methods
The classification of matter at a glance
The dividing line. A mixture is split by physical means (filtration, distillation, chromatography); a compound is split only by a chemical change, and always returns the same elements in the same fixed ratio.
Section 1-2

Measurement and the SI Units

Chemistry is a quantitative science, so every property is a number with a unit. The SI system rests on seven base units; everything else is derived from them. Mass in kilograms, length in metres and amount of substance in moles are the three that dominate this chapter.

QuantitySI base unitSymbol
Lengthmetrem
Masskilogramkg
Timeseconds
TemperaturekelvinK
Amount of substancemolemol
Electric currentampereA
Luminous intensitycandelacd
! Precision is not accuracy

Accuracy is how close a reading is to the true value; precision is how close repeated readings are to one another. A measurement can be precise yet inaccurate (a mis-calibrated balance) — both must be controlled before a result is trusted.

Section 1-3

Significant Figures & Dimensional Analysis

The significant figures of a measurement are the digits known with certainty plus one estimated digit. They record how good the measurement is, and they must survive the arithmetic.

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The counting rules
All non-zero digits count; zeros between them count; leading zeros never count; trailing zeros count only after a decimal point.

In \(\times,\div\) the answer keeps the fewest significant figures of any factor; in \(+,-\) it keeps the fewest decimal places. Exact (counted or defined) numbers carry infinite significant figures.

Dimensional analysis (the factor-label method) converts units by multiplying with ratios equal to one, so unwanted units cancel like algebraic symbols:

Factor-label example
\[ 2.5\ \text{km}\times\frac{1000\ \text{m}}{1\ \text{km}}\times\frac{100\ \text{cm}}{1\ \text{m}}=2.5\times10^{5}\ \text{cm} \]
Each ratio equals one, so the value is unchanged — only the unit is rewritten.
Section 1-4

The Laws of Chemical Combination

Five empirical laws, discovered before atoms were understood, govern how elements combine. They are the experimental bedrock that Dalton's theory was built to explain.

Conservation of mass

(Lavoisier) Mass is neither created nor destroyed in a chemical change — total mass of reactants equals total mass of products.

Definite proportions

(Proust) A given compound always contains the same elements in the same fixed proportion by mass, however it is prepared.

Multiple proportions

(Dalton) When two elements form more than one compound, the masses of one that combine with a fixed mass of the other are in a small whole-number ratio.

Reciprocal proportions

(Richter) The mass ratio in which two elements combine with a third is the same as, or a simple multiple of, the ratio in which they combine with each other.

Gaseous volumes

(Gay-Lussac) Gases react in volumes that bear a simple whole-number ratio to one another and to the gaseous products, at the same temperature and pressure.

Avogadro's law

Equal volumes of all gases, at the same temperature and pressure, contain an equal number of molecules — the key that turned Gay-Lussac's volumes into molecular ratios.

Section 1-5

Dalton's Atomic Theory

In 1808 John Dalton unified those laws with a single picture of matter built from indivisible particles.

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The postulates
Matter is made of tiny, indivisible atoms; atoms of an element are identical in mass; compounds form by atoms combining in fixed small whole-number ratios; atoms are merely rearranged — never created, destroyed or changed — in a reaction.

Conservation of mass follows from atoms being conserved; definite and multiple proportions follow from fixed whole-number combining ratios. Later work refined the theory — atoms are divisible, and isotopes show atoms of an element can differ in mass — but the framework still underpins all of chemistry.

Section 1-6

Atomic and Molecular Masses

Atoms are too light to weigh individually, so masses are quoted relative to a standard. The unified atomic mass unit \(1\,\text{u}\) is defined as exactly one-twelfth of the mass of a carbon-12 atom, so \(1\ \text{u}=1.66\times10^{-24}\ \text{g}\).

Because most elements are mixtures of isotopes, the average atomic mass is a weighted mean of the isotopic masses. The molecular mass of a substance is the sum of the atomic masses of its atoms; for ionic compounds, where no discrete molecule exists, we use the formula mass instead.

The pattern

The molecular mass of water \(\ce{H2O}\) is \(2(1.008)+16.00=18.02\ \text{u}\); the formula mass of \(\ce{NaCl}\) is \(22.99+35.45=58.44\ \text{u}\).

Section 1-7

The Mole Concept

Chemists count atoms by weighing. The bridge between the macroscopic gram and the invisible atom is the mole — the amount of substance containing as many entities as there are atoms in \(12\ \text{g}\) of carbon-12. That number is Avogadro's number:

Avogadro's constant
\[ N_A = 6.022\times10^{23}\ \text{mol}^{-1} \]
One mole of anything contains \(6.022\times10^{23}\) of those entities — atoms, molecules, ions or electrons.

The mass of one mole, in grams, is the molar mass \(M\), numerically equal to the atomic or molecular mass in u. The mole sits at the centre of a three-way conversion that solves nearly every quantitative problem in the chapter.

MOLES n Mass grams ÷ M × M Particles N × Nₐ ÷ Nₐ Gas volume at STP ÷ Vₘ
The mole is the hub: every quantity passes through it
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The master bridge
\(n=\dfrac{m}{M}=\dfrac{N}{N_A}=\dfrac{V}{V_m}\)

Here \(m\) is mass, \(M\) molar mass, \(N\) the number of particles, \(V\) the gas volume and \(V_m\) the molar volume. For an ideal gas, \(V_m=22.7\ \text{L mol}^{-1}\) at STP (\(273.15\ \text{K},\ 1\ \text{bar}\)), and the older \(22.4\ \text{L mol}^{-1}\) at \(1\ \text{atm}\).

Section 1-8

Percentage Composition, Empirical & Molecular Formula

The empirical formula gives the simplest whole-number ratio of atoms; the molecular formula gives the actual numbers. They are linked by a single integer \(k\):

Empirical to molecular
\[ \text{Molecular formula}=k\times(\text{Empirical formula}),\qquad k=\frac{\text{Molar mass}}{\text{Empirical formula mass}} \]
For benzene \(\ce{C6H6}\), the empirical formula is \(\ce{CH}\) and \(k=6\).
The recipe. From percentage composition: (1) treat each percent as grams, (2) divide by atomic mass to get moles, (3) divide all by the smallest to get a ratio, (4) clear fractions to whole numbers — that is the empirical formula. Then use \(k\) to scale up to the molecular formula.
Section 1-9

Stoichiometry & the Limiting Reagent

A balanced equation is a recipe in moles. Its coefficients give the exact mole ratios in which substances react and form, so any quantity of one species can be converted to any quantity of another by passing through moles.

A worked ratio
\[ \ce{N2 + 3H2 -> 2NH3} \]
One mole of \(\ce{N2}\) reacts with three of \(\ce{H2}\) to give two of \(\ce{NH3}\) — the coefficients are the conversion factors.
! The limiting reagent decides the yield

When reactants are not supplied in the exact stoichiometric ratio, one runs out first — the limiting reagent. It alone fixes how much product forms; the others are in excess and partly remain. To find it, convert every reactant to moles, divide each by its coefficient, and the smallest quotient marks the limiting reagent.

Section 1-10

Ways to Express Concentration

The composition of a solution can be reported in several equivalent ways. The temperature-independent ones (molality, mole fraction, mass percent) are preferred for precise work, since molarity changes as a solution expands or contracts with temperature.

TermDefinitionNote
Mass percent\(\dfrac{\text{mass of solute}}{\text{mass of solution}}\times100\)temperature-independent
Mole fraction \(x\)\(\dfrac{n_{\text{component}}}{n_{\text{total}}}\)\(x_A+x_B=1\)
Molarity \(M\)\(\dfrac{\text{moles of solute}}{\text{volume of solution (L)}}\)varies with temperature
Molality \(m\)\(\dfrac{\text{moles of solute}}{\text{mass of solvent (kg)}}\)temperature-independent
ppm\(\dfrac{\text{mass of solute}}{\text{mass of solution}}\times10^{6}\)very dilute solutions
Dilution shortcut. Adding solvent changes the volume but not the moles of solute, so \(M_1V_1=M_2V_2\) for any dilution.
Worked Examples

Putting It to Work

1 Significant figures in a calculation

Problem. A metal sample of mass \(36.6\ \text{g}\) occupies \(2.0\ \text{cm}^3\). Report its density with correct significant figures.

Solution. Density \(=\dfrac{m}{V}\). The factor \(2.0\) has only two significant figures, so the answer is limited to two:

Working
\[ \rho=\frac{36.6}{2.0}=18.3\to 18\ \text{g cm}^{-3} \]
2 Testing the law of multiple proportions

Problem. In \(\ce{CO}\), \(12\ \text{g}\) of carbon combines with \(16\ \text{g}\) of oxygen; in \(\ce{CO2}\) with \(32\ \text{g}\). Do these obey the law?

Solution. For a fixed \(12\ \text{g}\) of carbon, the oxygen masses are in the ratio

Working
\[ 16:32=1:2 \]

A simple whole-number ratio — the law of multiple proportions holds.

3 Counting particles from mass

Problem. How many molecules, and how many atoms, are present in \(4.4\ \text{g}\) of carbon dioxide?

Solution. Molar mass of \(\ce{CO2}=44\ \text{g mol}^{-1}\), so \(n=\dfrac{4.4}{44}=0.1\ \text{mol}\):

Working
\[ N=0.1\times6.022\times10^{23}=6.022\times10^{22}\ \text{molecules} \]
\[ \text{atoms}=3\times6.022\times10^{22}=1.807\times10^{23} \]
4 From percentage to molecular formula

Problem. A compound is \(40\%\ \ce{C}\), \(6.7\%\ \ce{H}\) and \(53.3\%\ \ce{O}\) by mass, with molar mass \(180\ \text{g mol}^{-1}\). Find its molecular formula.

Solution. Convert percent to moles, then to a ratio:

Working
\[ \ce{C}:\tfrac{40}{12}=3.33,\quad \ce{H}:\tfrac{6.7}{1}=6.7,\quad \ce{O}:\tfrac{53.3}{16}=3.33 \]
\[ \text{ratio }=1:2:1\ \Rightarrow\ \text{empirical }\ce{CH2O}\ (30\ \text{u}),\quad k=\tfrac{180}{30}=6 \]

The molecular formula is \(\ce{C6H12O6}\) — glucose.

5 A limiting-reagent calculation

Problem. \(28\ \text{g}\) of \(\ce{N2}\) reacts with \(3\ \text{g}\) of \(\ce{H2}\) to form ammonia. Which is limiting, and what mass of \(\ce{NH3}\) forms?

Solution. Moles: \(\ce{N2}=\tfrac{28}{28}=1\), \(\ce{H2}=\tfrac{3}{2}=1.5\). The recipe \(\ce{N2 + 3H2 -> 2NH3}\) needs \(3\) mol \(\ce{H2}\) per mol \(\ce{N2}\); only \(1.5\) mol is present, so \(\ce{H2}\) is limiting:

Working
\[ n_{\ce{NH3}}=\frac{2}{3}\times1.5=1\ \text{mol}\ \Rightarrow\ m=1\times17=17\ \text{g} \]

Half the nitrogen \((0.5\ \text{mol},\ 14\ \text{g})\) is left over in excess.

6 Molarity and dilution

Problem. \(5.85\ \text{g}\) of \(\ce{NaCl}\) is dissolved to make \(500\ \text{mL}\) of solution. Find its molarity, then the volume of water needed to dilute it to \(0.05\ \text{M}\).

Solution. \(n=\tfrac{5.85}{58.5}=0.1\ \text{mol}\), so

Working
\[ M=\frac{0.1}{0.500}=0.2\ \text{M} \]
\[ M_1V_1=M_2V_2:\quad V_2=\frac{0.2\times500}{0.05}=2000\ \text{mL} \]

So add \(2000-500=1500\ \text{mL}\) of water.

Review

Chapter Summary

Matter

Pure substances (elements, compounds) versus mixtures (homogeneous, heterogeneous); mixtures separate physically, compounds chemically.

Measurement

Seven SI base units; significant figures track precision; dimensional analysis converts units by cancellation.

The laws

Conservation of mass, definite, multiple and reciprocal proportions, gaseous volumes — all explained by Dalton's atoms.

The mole

\(n=\dfrac{m}{M}=\dfrac{N}{N_A}=\dfrac{V}{V_m}\) with \(N_A=6.022\times10^{23}\).

Formulae

Empirical is the simplest ratio; molecular \(=k\times\) empirical, with \(k=\tfrac{M}{\text{emp. mass}}\).

Stoichiometry

Coefficients are mole ratios; the limiting reagent fixes the yield; concentration is molarity, molality or mole fraction.

Practice

Problems

Identify what is asked, route everything through the mole, and keep the significant figures honest. Difficulty rises down the list. Take atomic masses as \(\ce{H}=1,\ \ce{C}=12,\ \ce{N}=14,\ \ce{O}=16,\ \ce{Na}=23,\ \ce{S}=32,\ \ce{Cl}=35.5,\ \ce{Ca}=40\).

  1. Express \(0.00204\ \text{kg}\) in grams and state the number of significant figures.
  2. How many moles, and how many atoms, are there in \(11.5\ \text{g}\) of sodium?
  3. Calculate the mass of \(0.25\ \text{mol}\) of \(\ce{CaCO3}\).
  4. A gas occupies \(5.6\ \text{L}\) at STP (\(1\ \text{atm}\)). How many moles and how many molecules does it contain?
  5. Copper forms two oxides containing \(79.9\%\) and \(88.8\%\) copper. Show these obey the law of multiple proportions.
  6. Find the empirical formula of a compound that is \(70\%\ \ce{Fe}\) and \(30\%\ \ce{O}\) by mass.
  7. A hydrocarbon contains \(85.7\%\) carbon and has molar mass \(56\ \text{g mol}^{-1}\). Find its molecular formula.
  8. What mass of \(\ce{CO2}\) is produced when \(10\ \text{g}\) of \(\ce{CaCO3}\) is completely decomposed, \(\ce{CaCO3 -> CaO + CO2}\)?
  9. Calculate the molarity of a solution made by dissolving \(4.9\ \text{g}\) of \(\ce{H2SO4}\) in water to make \(250\ \text{mL}\) of solution.
  10. How many millilitres of \(0.5\ \text{M}\) \(\ce{HCl}\) are needed to prepare \(100\ \text{mL}\) of \(0.1\ \text{M}\) \(\ce{HCl}\)?
  11. In the reaction \(\ce{2H2 + O2 -> 2H2O}\), \(4\ \text{g}\) of \(\ce{H2}\) is mixed with \(32\ \text{g}\) of \(\ce{O2}\). Identify the limiting reagent and find the mass of water formed.
  12. A \(6.8\%\) by mass aqueous solution of \(\ce{H2O2}\) has density \(1.0\ \text{g mL}^{-1}\). Find its molarity and the mole fraction of \(\ce{H2O2}\).
Tip: almost every numerical problem in this chapter is solved by the same move — convert what you are given into moles, use the balanced equation or formula to step to the moles of what you want, then convert back to grams, particles or volume. Keep the units attached at every step and they will police your arithmetic for you.