Two Principal Types of Elements

Metals
Chapter 3 – Metal atoms tend to lose one or more
electrons
– Metals form cations
Chemical Compounds Nonmetals
– Nonmetal atoms tend to gain one or more
electrons
– Nonmetals form anions

Metalloids – either tend to lose or tend to gain electrons

Noble Gases – neither tend to lose nor tend to gain electrons

1 2

Three Principal Types of Bonding Chemical Formulae

Molecular Compounds
• Covalent Bonding
• Chemical Formula for a chemical entity of
– Electron Sharing between Nonmetals
a compound: symbolic representation that,
• Ionic Bonding at minimum, indicates:
– Electron Transfer from Metals to Nonmetals – the elements present
• Metallic Bonding – the relative number of atoms of each element
– Electron Sharing between Metals • Molecular Compound: composed of
• The borders between types of bonds are not sharp, but are rather discrete units called molecules.
fuzzy. The same as the periodic table cannot sharply be divided
into metals and nonmetals – as exemplified by the existence of – bonds that keep a molecule together are
semimetals or metalloids – some chemical bonds are at the covalent bonds
borderline between two basic types.

3 4

1
 Different Types of Formulae Different Types of Formulae
Empirical and Molecular Structural
O Structural formula: shows the order in which atoms
H are bonded together in a molecule (but not the shape
H
C C of a molecule), and what types of bonds are present:
H OH
Acetic Acid
C=O double bond
• Empirical formula: shows types of atoms present Identical
and their ratios. Preferably, empirical formulae structural
formulae C−O single bond
are expressed as simplest formulae: CH 2O
– in a simplest formula, the atomic subscripts are
reduced to the smallest whole number ratios
• Molecular formula: formula of an actual molecule Condensed structural formula: a molecular formula in
of that compound: C 2H 4O 2 which connectivity is preserved: CH 3COOH

5 6

Structural Formulae Molecular Models

Expanded and Condensed Molecular Shape
Structural formulae only show the order in which atoms
A molecular model is based on a molecular formula, and
are bonded together in a molecule. They might appear as represents the three-dimensional arrangement of atoms:
different, although they contain the same information: Acetic Acid
CH3 CH CH2 OH H3C CH2 CH CH2 OH

CH3
CH2 CH3

Both formulae have the

same connectivity profile:

Both structural formulae are represented by the same Ball and Stick Space-Filling
condensed structural formula: CH3(CH)(C2H5)(CH2OH)
Molecular Model Molecular Model

7 8

2
 Molecular Models Molecular Models
Molecular Shape and Molecular Size Relation to Molecular Formulae

Acetic Acid
Free Nuclear
Atoms Atom

Bound
Atoms
Space Filling Ball & Stick
emphasizes electrons emphasizes
nuclei
Spatial Formula or
radii of atom spheres proportional to radii of atoms Ball and Stick Stereochemical Formula:
Overlapping Spheres à Sharing of Electrons à formula that indicates the spatial
Molecular Model
Covalent Bonding arrangement of atoms or atomic
groups in a molecule

9 10

Different Types of Formulae Chemical Formulae

Spatial An Application
Spatial Formula or Stereochemical Formula For the compound Ge[S(CH 2)4CH 3]4, determine (a) the number of
atoms in one formula unit (b) the ratio, by number, of C atoms to
H atoms, and (c) the ratio, by mass, of Ge to S.
§ A simple straight line represents a
bond lying approximately in the structural
surface plane formula
§ A wedge shaped bond is directed
in front of this plane (thick end Convert the condensed structural formula into a molecular formula:
toward the viewer) Ge[S(CH2)4CH3]4 = Ge[SC4H8CH3]4 = Ge[SC5H11]4 = GeS4C20H44
§ A hatched bond is directed in back
of this plane (away from the (a) #atoms 1 + 4 + 20 + 44 = 69
viewer) (b) #C/#H = 20/44 = 5/11 = 0.4545
(c) mGe/mS = 72.61u / 4×32.07u = 72.61/128.28 = 0.5660

11 12

3
 Ionic Compounds Ion Ensembles
• An ionic compound is often referred to as a salt; Due to opposite charges, cations and anions attract and
form ion pairs. But upon attraction, charge is not completely
positive cations and negative anions are joined
quenched, and ion pairs form larger units:
together by electrostatic forces of attraction:
+ and − + −
+ -
Na Cl

• cations and anions pack into orderly arrays in

solids; they become mobile when the compound
melts
– in general, compounds of metals and nonmetals are ionic:
metals form cations; nonmetals form anions
Ion Pairs Ion Clusters Ion Crystal

13 14

Masses of Elemental Units The Mole Concept

Formula Mass ([Link].): mass of a formula unit
(preferably the simplest empirical formula) Measurable properties depend on the number of
in atomic mass units: entities: The mole concept provides a link between
for the ionic compound magnesium chloride: microscopic properties relating to atoms and
[Link].(MgCl2) = AW(Mg) + [Link](Cl)
= 24.31 u + 2. (35.45 u) = 95.21 u molecules, and macroscopic properties relating to
Molecular Mass ([Link].): mass of a molecule elements and compounds:
(molecular formula) in atomic mass units:
for the molecular compound water: mass of one molecule of H2O: 2·mH+mO = 18.02 u
[Link].(H2O) = [Link](H)+ AW(O)
= 2. (1.01 u) + 16.00 u = 18.02 u molar mass of H2O: 18.02 u·NA =18.02 g/mol
Molar Mass M: mass of one mole of compound – mass of one unit of MgCl2: mMg + 2·mCl = 95.21 u
atomic mass unit u turns into g/mol:
one mole MgCl2 = 95.21 g/mol × 1 mol = 95.21 g molar mass of MgCl2: 95.21 u·NA = 95.21 g/mol
one mole H2O = 18.02 g/mol × 1 mol = 18.02 g

15 16

4
 Mole of an Element Ratios of Masses
For active nonmetals, naturally occurring elemental Ratio of Masses are intensive properties, and thus
forms are compositions of molecules, rather than of are characteristic for chemical compounds.
atoms: Law of Definite Proportions: mass ratios of different
H2 O2 N2 F2 Cl2 Br2 I2 P4 S8 elements within the same compound.
Law of Multiple Proportions: mass ratios of a same
Seven Diatomics – honclbrif element within different compounds.
Fraction of Mass fm: mass of a specified entity over
The phrase one mole of hydrogen appears the total mass of the compound containing that entity
ambiguous – does this mean one mole of
hydrogen atoms (1 mol H) or one mole of Percent Composition: if not further specified, percent
hydrogen molecules (1 mol H 2)? But in Some molecular forms of composition refers to a composition by mass:
general, one mole hydrogen refers to one elemental phosphorus
mole of the element hydrogen, 1 mol H 2. and elemental sulfur %m = fm ×100%
17 18

Percent Composition Percent Composition

Illustration Guide to Empirical Formulae
Percent Composition by mass of A compound was found to contain 20.0% H and 80.0% C by
fluorine in halothane, C2HBrClF3, mass. Determine its simplest empirical formula:
1. Choose any convenient amount of compound, say 100 g, and
an inhalational general anesthetic: determine the relative mass of each element: 20.0 g H; 80.0 g C
2. Convert masses to moles:
1. Determine the molar mass M: 20.0 g 80.0 g
mole(H) = = 19.80 mol mole(C) = = 6.66 mol
M = 2 ⋅ MC + MH + MBr + MCl + 3 ⋅ MF = 197.38 g mol 1.01 g/mol 12.01 g/mol
3. Establish a tentative empirical formula: C6.66 H19.8
4. Divide each subscript by the smallest: CH2.97
2. Calculate fraction of mass and percent composition: 5. Round off fractional subscripts to the nearest ratio of small whole
numbers; absolute changes should be close to 1.0%:
fm(F) = (3 ⋅19.00) g mol 197.38 g mol = 0.2888 2.97 ≈ 3 = 3/1 (|3−2.97| = 0.03; 0.03/2.97 = 1.0%)
%m(F) = 0.2888 ×100% = 28.88% CH 3 – simplest empirical formula
6. If the situation requires that there be no broken number subscripts,
Percent Composition – Law of Definite Proportions in Action multiply all subscripts by a small number chosen to make them all
integral.

19 20

5
 Rounded Subscripts Percent Composition
Ratios of Small Whole Numbers Moles and Masses
Two Tentative Formulae, CH2.97, and CH2.65: Round off An oxide of phosphorous contains 28.6% P and 71.4% O on a mole
fractional subscripts to the nearest ratio of small whole basis. Determine the simplest empirical formula, and its mass
numbers; changes should be close to 1.0%. composition:
CH2.97 ≈ CH3 1. Begin with one mole of the oxide, evaluate moles of P and O,
and set up a tentative empirical formula:
2.97 + 0.03 = 3.00 = 3/1; 0.03/2.97 = 0.010 = 1.0% ✔ n P = 0.286 mol; n O = 0.714 mol; P 0.286O 0.714
CH2.65 = CH265/100 = CH53/20 not a ratio of small whole numbers 2. Divide by the smallest subscript, evaluate small whole number
CH2.65 ≈ CH3 subscripts, and construct the simplest formula:
P 1.00O 2.50 = P 1O 5/2 = P 2O 5
2.65 + 0.35 = 3.00 = 3/1; 0.35/2.65 = 0.132 = 13.2% ✗
3. Calculate the mass composition based on one mole of compound:
CH2.65 ≈ CH2.50 ≈ CH5/2 = C2H5
MW (P2O5 ) = 2mol ⋅ 30.97g ⋅ mol −1 + 5mol ⋅16.00g ⋅ mol −1 = 141.94g ⋅ mol −1
2.65 − 0.15 = 2.50 = 5/2; 0.15/2.65 = 0.057 = 5.7% ✗
fm(P) = 2mol ⋅ 30.97g ⋅ mol −1 1mol ⋅ MW = 61.94g 141.94g = 0.436 %m(P) = 43.6%
CH2.65 ≈ CH2.67 ≈ CH8/3 = C3H8 fm(O) = 5mol ⋅16.00g ⋅ mol −1 1mol ⋅ MW = 80.00g 141.94g = 0.564 %m(O) = 56.4%
2.65 + 0.02 = 2.67 = 8/3; 0.02/2.65 = 0.008 = 0.8% ✔

21 22

Combustion Analysis Combustion Process

Principles Complete Combustion
Combustion Analysis is used to establish empirical
O2
formulae, to verify proposed formulae, or to establish
the purity of compounds
Elements accessible to combustion analysis are the
nonmetals carbon (C à CO 2), hydrogen (H à H 2O),
sulfur (S à SO 2), and nitrogen (N à NO, NO2)
Water:
Hà H2 O H 2O ß H
(water)
collected in an absorber filled with magnesium perchlorate, Mg(ClO4 )2 .
collected in an absorber filled with magnesium perchlorate, Mg(ClO4 )2 (s)
mol (H) = 2 × mol (H2O) fm(H H 2 O) = 2 ×1.01 18.02 = 0.1121
mass(H) = 11.21% mass(H2O) ; moles(H) = 2×moles(H 2 O)
Setup for Carbon Dioxide: CO2 ß C
CH-analysis Cà CO 2 (carbon dioxide)
collected in an absorber filled with sodium hydroxide, NaOH.
using combustion collected in an absorber filled with sodium hydroxide, NaOH(s)
mol (C) = mol (CO2)
mass(C) = 27.29% mass(CO 2 ) ; moles(C) = moles(CO2 )

incomplete combustion: C à CO (carbon monoxide)

23 24

6
 Combustion Analysis Combustion Analysis
Application by Mole Application by Mass
0.658 g of compound XOX110 that contains carbon, hydrogen and oxygen, is 0.658 g of compound XOX110 that contains carbon, hydrogen and oxygen, is
burned in excess O2 . Produced are 1.285 g CO2 (MW: 44.01) and 0.652 g burned in excess O2 . Produced are 1.285 g CO2 (27.29% C), and 0.652 g
H2 O (MW: 18.02). Determination of its simplest empirical formula: H2 O (11.21% H). Determination of its simplest empirical formula:
1mol CO2 1mol C
carbon content from CO2 : nC = 1.285gCO2 × × = 0.02920 mol mC = 27.29%mCO = 0.2729 ×1.285g = 0.3507g
44.01gCO2 1mol CO2 2

mC = 0.02920 mol ×12.01 g ⋅ mol −1 = 0.3507g

mH = 11.21%mH O = 0.1121× 0.652g = 0.0731g
2
hydrogen content from H2 O: 1mol H2O 2 mol H
nH = 0.652g H2O × × = 0.0724 mol
18.02g H2O 1mol H2O mO = msample − mC − mH = 0.658g − 0.3507g − 0.0730g = 0.234g
mH = 0.0724 mol ×1.01 g ⋅ mol −1 = 0.0731g
nC = 0.3507g 12.01g ⋅ mol −1 = 0.02920 mol
oxygen content from conservation of mass: mXOX 110 = mC + mH + mO
mO = 0.658g sample − 0.3507g C − 0.0730g H = 0.234 g nH = 0.0731g 1.01g ⋅ mol −1 = 0.0724 mol
nO = 0.234g 16.00g ⋅ mol = 0.0146 mol
−1
nO = 0.234g 16.00g ⋅ mol −1 = 0.0146 mol

simplest formula: C0.02920H0.0724O0.0146 ⇒ C2.00H4.96O1.00 ⇒ C2H5O simplest formula: C0.02920H0.0724O0.0146 ⇒ C2.00H4.96O1.00 ⇒ C2H5O

25 26

Combustion Analysis Combustion Analysis

Mass Balance Conservation of Mass
When burned in an excess of oxygen, compounds of the C10 When burned in an excess of oxygen, compounds of the C10
series yield carbon dioxide and water as the sole products. series yield carbon dioxide and water as the sole products.
1.024g of C10e produces 3.213g of CO2 (MW: 44.01) and 1.313g 1.223g of C10a produces 3.125g of CO2 (MW: 44.01) and 1.279g
of H2O (MW: 18.02): of H2O (MW: 18.02):
1mol CO2 1mol C 1mol CO2 1mol C
nC = 3.213gCO2 × × = 0.0730 mol nC = 3.125gCO2 × × = 0.0710 mol
44.01gCO2 1mol CO2 44.01gCO2 1mol CO2
mC = 0.0730 mol ×12.01g ⋅ mol −1 = 0.877g mC = 0.0710 mol ×12.01g ⋅ mol −1 = 0.853g
1mol H2O 2 mol H 1mol H2O 2 mol H
nH = 1.313g H2O × × = 0.146 mol nH = 1.279g H2O × × = 0.142 mol
18.02g H2O 1mol H2O 18.02g H2O 1mol H2O
mH = 0.146 mol ×1.01g ⋅ mol −1 = 0.147g H mH = 0.142 mol ×1.01g ⋅ mol −1 = 0.143g H

Mass Balance: mC10e − mC − mH = 1.024g − 0.877g − 0.147g = 0.000g ✓ Mass Balance: mC10a − mC − mH = 1.223g − 0.853g − 0.143g = 0.227g ✗
Remainder must be Oxygen: nO = 0.227 g 16.00g ⋅ mol −1 = 0.0142 mol
Simplest Formula for C10e: C0.0730H0.146 = CH2
Simplest Formula for C10a: C0.0710H0.142O0.0142 = C5H10O
€

27 28

7
 Mass Ratios Quantitative Elemental Analysis
Key to Empirical Formulae Principles
The compound sulfur dicyanide, C 2N 2S, contains 28.6% C, 33.3% N, Quantitative Elemental Analysis: All elements of a
and 38.1% S by mass. 0.236 g of a compound, claimed to be C 2N 2S,
is subjected to complete combustion, which yields 0.179 g carbon
compound are converted into well-defined products, the
dioxide (27.29% C). Thermal decomposition of 0.736 g of the same basis for a complete empirical formula determination.
compound produces 0.176g N 2(g). Is this really C 2N 2S?
Verify – Check Mass%: Needed are a complete list of constituting elements (qualitative
elemental analysis), mass of a sample, and masses of
mC = 27.29%mCO = 0.2729 × 0.179g = 0.0488g
2
products such as m(CO2), m(H2O), m(SO2), m(N2) or m(NH3)
m%(C) = (mC / msample ) ×100 = (0.0488g / 0.236g) ×100 = 20.7%
m%(N) = (mN / msample ) ×100 = (0.176g 0.736g) ×100 = 23.9% N elements require N−1 products: mass and moles of
m%(S) = 100% − m%(C) − m%(N) = (100− 20.7 − 23.9)% = 55.4% the remaining element are obtained via mass difference
Different Mass Composition: Identify by empirical formula based on 100g: (law of conservation of mass). Results of different
nC = 20.7 / 12.01= 1.72mol nN = 23.9 / 14.01= 1.71mol
experiments are linked via the law of definite proportions,
nS = 55.4 / 32.06 = 1.73mol for example by percent composition.
C1.72N1.71S1.73 = C1.01N1.00S1.01 = CNS Different Compound

29 30

Quantitative Elemental Analysis Quantitative Elemental Analysis

Combination of Results Complete Empirical Formula
L-Alanine, a CHNO-compound, is one of the 20 amino acids encoded by the genetic
L-Alanine, a CHNO-compound, is one of the 20 amino acids code. Subjected to combustion analysis, a 0.2350 g sample of L-Alanine produces
encoded by the genetic code. Combustion analysis of 0.2350 g 0.3482 g carbon dioxide and 0.1664 g water. In a second experiment, the nitrogen
of L-Alanine produces 0.3482 g carbon dioxide and 0.1664 g content of 0.7394 g L-Alanine is converted into 0.1163 g N2(g).
water. In a second experiment, the nitrogen content of 0.7394 g 1 st sample: 36.97 mg N = 2.639 mmol N
L-Alanine is converted into 0.1163 g N2(g). Combustion Analysis: carbon and hydrogen content of 1 st sample:
The second experiment provides information for only one element. Begin with m(C) = 7.912mmol ×12.01g / mol = 95.02mg
n(C) = n(CO2 ) = 0.3482g 44.01g ⋅ mol −1 = 7.912mmol
the second experiment, and evaluate the mass contribution of nitrogen:
n(H) = 2 ⋅ n(H2O) = 2 × 0.1664g 18.02g ⋅ mol −1 = 18.47mmol m(H) = 18.47mmol ×1.01g / mol = 18.65mg
N (2nd sample) :
Conservation of Mass: oxygen content of 1 st sample:
fm(N) = 0.1163g / 0.7394g = 0.1573 %m(N) = 0.1573 ×100% = 15.73%
m(O) = m(tot) − m(C) − m(H) − m(N) = 235.0mg − 95.02mg −18.65mg − 36.97mg = 84.36mg
Use this result and determine the nitrogen content of the first sample:
n(O) = 84.36mg 16.00g ⋅ mol −1 = 5.273mmol
N (1st sample) :
Simplest Formula: C7.912H18.47N2.639O5.273 = C2.998H6.999N1.000O1.998
mN = fm(N) ⋅ msample = 0.1573 ⋅ 0.2350g = 0.03697g = 36.97mg
Empirical Formula of L-Alanine: C3H7NO2
nN = 36.97mg / 14.01g ⋅ mol = 2.639mmol
−1

31 32

8
 Mass Spectrometry Mass Spectrometry
Key to Molecular Information Molecular Mass
Mass Spectrum of XOX110
separation detection
m/z precision of ones
Magnet
ionization
sample Largest m/z ratio: M+

relative intensity
Molecular Weight

acceleration
intensity

deflection

Molecular Ion M +: ion obtained Small peak at 91u

13
when the molecule loses but m/z C isotope
one electron m/z: mass/charge ratio Largest m/z ratio: Molecular Weight
MW – 90u

33 34

Chemical Formulae Mass Spectrometry

Empirical and Molecular Molecular Formula
Compound XOX110 − simplest empirical formula the two compounds of the C10 series:
obtained from combustion analysis: C 2H 5O C10a
Formula Mass ([Link].): 2 ⋅12.01+ 5 ⋅1.01+16.00 = 45.07u ≈ 45u Simplest Formula – C5 H10 O
Formula weight: ≈ 86u
Compound XOX110 − molecular mass ([Link].): 90u MW/FW:≈2
MW ≈172u Molecular Formula – C10 H20 O2
(determined by mass spectrometry)
mass ratios: molecular/empirical = [Link]./[Link].
C10e
Simplest Formula – CH2
Formula weight: ≈ 14u
n = 2: molecular formula: (C 2H 5O)2 MW/FW:≈10
MW ≈140u Molecular Formula – C10 H20
C4H10O 2
35 36

9
 Mass Spectrometry Oxidation States
Isotopes
The degreasing agent Perklone™ is a carbon-chlorine compound with a • Oxidation State or oxidation number relates to
chlorine content of 85.55% by mass. Its mass spectrum is shown below.
Determine its molecular formula. For a 100.0g sample:
the hypothetical charge of an atom due to the
nCl = 85.55g 35.45g ⋅ mol −1 = 2.412mol ; nC = 14.45g 12.01g ⋅ mol −1 = 1.203mol
number of electrons an atom loses, gains, or
otherwise appears to use in joining with other
Empirical Formula: atoms in compound formation.
C1.203Cl 2.412 = C1.000Cl 2.005 = CCl 2 • Oxidation State values generally follow sensible
Formula Weight: and understandable trends, but their overall
2×35.45 + 12.01 = 82.91 ≈ 83 u usefulness is for book-keeping: As long as
Molecular Weight: ≈165 u
consistent assignment rules are adopted,
MW/FW: ≈2 changes in oxidation state values might be
employed to account for movement of electrons.
Molecular Formula – C2Cl4 Cl Isotopes: ≈ 76% 35Cl and 24% 37Cl

37 38

Seven Rules for Oxidation States Oxidation State Assignment

Fundamentals
1. The sum of the O.S. of all atoms within a chemical entity
equals the charge of that entity (conservation of charge) For ionic compounds, since the sum of the O.S. of all
2. The O.S. of an individual atom in any single-elemental form atoms within a chemical entity equals its charge, O.S. for
Increasing Significance

(e.g. Ni, Ne, N, N 2, C 60, Cl2, P 4, S 8 ...) is zero atoms within cations, as well as O.S. for atoms within
3. In compounds with other nonmetals, the O.S. of hydrogen anions are assigned individually (fragmentation of entities)
is +1, and in compounds with no other nonmetals, the
O.S. of hydrogen is −1
The O.S. of a monoatomic ion (cation or anion) is
4. In their compounds, group 1 metals have an O.S. of +1, and equal to its charge
group 2 metals have an O.S. of +2 Most often, all atoms of a particular element are given the
5. In its compounds, the O.S. of fluorine is −1 same O.S. It follows that O.S. are usually assigned as
6. In its compounds, the O.S. of oxygen is −2 average O.S., also called empirical O.S. These O.S. are
7. In compounds comprised of two types of elements only, first,
group 17 nonmetals are assigned an O.S. of −1, then, group 16
sufficient to account for the flow of electrons
nonmetals are assigned an O.S. of −2, and last, group 15 The O.S. of atoms and the corresponding empirical
nonmetals are assigned an O.S. of −3 formulae are interdependent

39 40

10
 Oxidation State Assignment Oxidation State Assignment
Application Presentation
An exemplary problem – determine the O.S. for all elements An exemplary problem – determine the O.S. for all elements
in sulfate anion, SO42− : in sulfate anion, SO42− :
1) Use rule #1, and formulate a defining oxidation state Summarize your results: O.S.(Oxygen) = −2 ; O.S.(Sulfur) = +6
equation DOSE: 1×O.S.(S) + 4×O.S.(O) = −2 !!
+6 −8
+6 −2
2) Work rules #2 to #7, in that order. Whenever a rule is O.S. might be written as over-scripts, but [S O4 ]2− ≠ [S O 4 ]2−
applicable to the problem at hand, assign an O.S. for a
particular element, and update the DOSE: ¬2−
+6 −2 O.S. per single atom of a given element
§ rule #6: O.S.(O) = −2
§ updated DOSE: 1×O.S.(S) + 4×(−2) = −2
S O4 Average O.S.
3) When O.S. have been assigned for all but one element,
use rule #1 and the updated DOSE and determine the ¬2−
+6 −8 sum of O.S. for all atoms of a given element
O.S. of the remaining atom or element:
§ 1×O.S.(S) + 4× (−2) = −2 à O.S.(S) − 8 = −2 àO.S.(S) = +6
(S ) (O ) 4 Group O.S.

41 42

Oxidation State Assignment Nitrogen – an O.S. Chameleon

Apparent Disagreements
Since O.S. are determined by sequential application of all seven
O.S. rules, the O.S. of an element in a particular molecule might
Rules 1 and 6
seem to disagree with the seven O.S. rules. Consider the oxidation
states of oxygen in Water (H 2O), and in Hydrogen Peroxide (H 2O 2): Rules 1 and 6
• Water H2O: Rules 1 and 6
– rule #1 DOSE: 1×O.S.(O) + 2×O.S.(H) = 0 Rules 1 and 6
– rule #3 O.S.(H) = +1; DOSE: 1×O.S.(O) + 2 (+1) = 0
– rule #1 O.S.(O) + 2 = 0 è O.S.(O) = −2
Rules 1 and 6
– In agreement with rule #6 Rules 1 and 2
• Hydrogen Peroxide H2O2: Rules 1, 3, and 6
– rule #1 DOSE: 2×O.S.(O) + 2×O.S.(H) = 0
Rules 1 and 3
– rule #3 O.S.(H) = +1; DOSE: 2×O.S.(O) + 2×(+1) = 0
– rule #1 2×O.S.(O) + 2 = 0 è O.S.(O) = −1 Rules 1 and 3
– In disagreement with rule #6

43 44

11
 Oxidation State Assignment Oxidation State Assignment
0
Inorganic Compounds Organic Compounds
P4 −4 1
C H4 Application of the O.S. rules results in
3 −2 Application of the O.S. rules results in empirical O.S.,
Al2 O3 empirical, or average O.S. For molecular
or average O.S. Non-integer oxidation numbers point −2 1
7 −2 compounds, individual O.S. for each atom
Mn O4 − to the fact that the formula unit is composed of two or C2 H4
4 −2 more subunits, in which the same element has a might be assigned by applying the O.S.
N O2 4 −2 rules to each pair of bound atoms:
different O.S.:
1 −1 C S2
Na H
1 3 −2
8/3 −2 3 −2 2 −2 0 1 −2
for empirical O.S.,
K N O2
2 −3
Fe3 O4 = Fe2 O3 •Fe O C2 H4 O2 convert condensed
C N− −8 3 1 structural formulae
Rule #1 into molecular
1 −2
NS − ? −2 2×4/3 −2 8/3 −2 C3 H8 formulae
3 −2 Fe3 O4 = Fe O4/3 = Fe O4/3 = Fe3 O4 4 3 −2 CH3 CH2 CH(OH)CH2 CHO
Fe2 S3
83
simplest empirical C3 O 2 C5 H10 O2
−6 5 1 −2

Fe3 O4
−2
empirical formula formula C 5 H10 O2

45 46

Oxidation State Assignment Oxidation State Assignment

Ionic Compounds Groups of Atoms
Determine the O.S. for all atoms in Ammonium Nitrate On occasion, the O.S. of more than one element remain
(NH 4+)(NO 3-): undefined. In such a case, one might assign group oxidation
states G.O.S. as basis for a second (order) DOSE.
NH4+ : O.S.(N) + 4×O.S.(H) = +1 ; O.S.(H) = 1 ; à O.S.(N) = -3
An exemplary problem – Determine O.S. for all elements in SOCl2 :

rule #1: DOSE: O.S.(S) + O.S.(O) + 2×O.S.(Cl) = 0

The nitrogen atoms have different O.S. in cation and anion rule #6: O.S.(O) = -2; DOSE: O.S.(S) +(-2) + 2×O.S.(Cl) = 0
Grouping: G.O.S.({SCl2}) -2 = 0 à G.O.S.({SCl2}) = 2
Compare with empirical O.S. in NH 4NO 3:
rule #1: DOSE: 1×O.S.(S) + 2×O.S.(Cl) = 2
2×O.S.(N) + 4×O.S.(H) + 3×O.S.(O) = 0 rule #7: O.S.(Cl) = -1; DOSE: O.S.(S) + 2×(-1) = 2
O.S.(H) = 1; O.S.(O) = -2; 2×O.S.(N) + 4 –6 = 0 à O.S.(N) = 1
rule #1: O.S.(S) -2 = 2 à O.S.(S) = 4
The nitrogen atoms have the same average O.S.
SOCl2: O.S.(Sulfur) = 4; O.S.(Oxygen) = −2; O.S.(Chlorine) = −1

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12
 Known Oxidation States Naming Compounds
Guide to Empirical Formulae Simple Essentials
When oxidation states of all atoms within a compound are Organic Compound: primarily composed of carbon and
known, a DOSE might be used to establish and/or complete hydrogen (e.g. CH4, C2H4, C6H6, C10H22). Might contain
an empirical formula. small amounts of other nonmetals such as oxygen,
an exemplary problem – derive an empirical formula for an oxoanion nitrogen, or sulfur (e.g. CH3OH, C2H5NH2, C6H5SCH3)
of sulfur with charge of 2-, and with a sulfur oxidation state of seven: Inorganic Compound: any combination of elements that
simple formula: S mO n2− (m, n: small whole numbers) does not fit the category of an organic compound (e.g. HF,
O.S.(O) = −2 (rule #6); O.S.(S) = 7 (additional information)
MgCl2, Fe2S3, CO2, H2O, NaCH3COO).
At the borderline: CH3COO− (organic), HCO3− (inorganic),
DOSE: m×O.S.(S) + n×O.S.(O) = −2 C10H10Fe (organometallic)
m×7 + n×(−2) = 7m −2n = −2 à 7m = 2n −2 = 2(n − 1) Binary Compound: composed of two elements (but not
7m = 2(n − 1) à m/(n − 1) = 2/7 (ratio of small whole numbers) restricted to two atoms: binary ≠ diatomic).
It follows that m = 2, and n − 1 = 7, or n = 8 Ternary Compound: composed of three elements (but not
restricted to three atoms: ternary ≠ triatomic).
Empirical Formula: S2O82− (Simplest Formula: SO4− )

49 50

Naming Compounds Naming Compounds

Elemental Cations Elemental Anions
cations inherit the names of their elements

Indicate the charge with a Roman numeral …

Rule of Thumb: … unless the element forms only one cation
Main Group Metals – Fixed Charge
charge is obtained according to the group number (Roman group numeral):
Group 1(IA): +1; Group 2(IIA): +2; Group 13(IIIA): +3 … Recall oxidation state rules three and seven

Transition Metals – Variable Charges When naming elemental anions, the stem of the element
if for a transition metal no charge indication is given, derive a charge name is kept, the ending is replaced by the suffix ide.
according to the (Roman) group number : Group 3(IIIB): +3 ; Group 12(IIB): +2
The O.S. of an elemental cation is equal to its charge The O.S. of an elemental anion is equal to its charge

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13
 Naming Compounds Naming Compounds
Monoatomic Ions Polyatomic Ions

Composition of a Bicarbonate: 330 PPM

Mineral Water Calcium: 170 PPM
Chloride: 170 PPM
Sulfate: 42 PPM
Sodium: 11 PPM
Magnesium: 6.0 PPM
Nitrate: 1.3 PPM
Potassium: 1.2 PPM
Fluoride: 0.16 PPM

53 54

Common Polyatomic Ions Seven Essential Polyatomics

ammonium • Ammonium NH4+
carbonate • Hydroxide OH−
hydrogen carbonate • Nitrate NO3−
or bicarbonate
• Sulfate SO42−
• Phosphate PO43−
• Carbonate CO32−
hydroxide • Hydrogen Carbonate HCO3−
nitrate or Bicarbonate HCO3− = CO2OH− = {CO2 + OH−}
phosphate six anions – one cation
six binary compounds – one ternary compound
five binary anions all of which contain oxygen
Three defining aspects: what is the second nonmetal,
sulfate
Petrucci – Table 3.5 how many oxygen, what is the charge

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 Naming Compounds Naming Compounds
Binary Acids Oxoacids
Acid: compound with acidic hydrogen(s)
H nE: binary acid of nonmetal element E
H nE = hydro element-ic acid
−
HF = hydrofluoric acid F = fluoride
−
HCl = hydrochloric acid Cl = chloride
−
HBr = hydrobromic acid Br = bromide
−
HI = hydroiodic acid I = iodide
2−
H 2S = hydrosulfuric acid S = sulfide
O.S. rule #7 is applicable, and defines their empirical formulae
Note: In all oxoacids, the acidic H is bonded to O. Formulae that
n×O.S.(H) + O.S.(E) = 0 ; n .1 + O.S.(E) = 0; n = − O.S.(E) explicitly reflect this are acceptable, e.g. HONO 2 instead of HNO 3

57 58

Seven Essential Acids Naming and Deriving Formulae

Ionic Compounds
• Hydrofluoric Acid HF
• Hydrochloric Acid HCl
• Hydrobromic Acid HBr
• Hydroiodic Acid HI
• Hydrosulfuric Acid H2S
• Sulfuric Acid H2SO4
Potassium Calcium
• Nitric Acid HNO3 Chloride Sulfide BaO: Barium Oxide
five binary acids – two oxoacids
five monoprotic acids – two diprotic acids
Copper(II) Aluminum
five strong acids (HCl, HBr, HI, HNO 3, H 2SO 4) Sulfate Sulfate
two weak acids (HF, H 2S) Ba(OH)2: Barium Hydroxide

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15
 Naming and Deriving Formulae Naming and Deriving Formulae
Covalent Compounds Hydrates
Hydrates are formed when inorganic compounds
incorporate water molecules into their solid state
arrangement:

The Element with the negative oxidation number

is designated with the anionic suffix “ide”

When performing stoichiometric calculations, water

carbon monoxide of hydration must be included in the molar mass.

61 62

Composition of Hydrates Mixtures with Hydrates

Mass Percent Mass Percent
Anhydrous (without water) Magnesium Perchlorate is a superior
Magnesium Perchlorate Mg(ClO4)2 (MW: 223.21) crystallizes as
hexahydrate. The mass percent water in Mg(ClO4)2Ÿ6 H2O drying agent for gas analysis. A sample of 2.542 g Mg(ClO 4)2 used in
combustion analysis gains 0.387 g in mass. The mass percent of
amounts to:
Mg(ClO 4)2Ÿ6 H 2O in the resulting mixture of anhydrous salt and
( )
%H2O = 6 ⋅18.02 g (223.21 g + 6 ⋅18.02 g) ×100% = 32.63% hexahydrate calculates as follows:
n(Mg(ClO4 )2 ) = 2.542g 223.21 g⋅ mol-1 =11.39mmol
A certain hydrate of Na2SO3 (MW: 126.04) contains almost
50% H2O (MW: 18.02) by mass. Formula of this compound: A sample of 2.542 g can bind 6×11.39 = 68.34 mmol water. Its gain in mass
of 0.387 g is due to absorbed water:
100g of hydrate contain ≈ 50 g of Na2SO3 and ≈ 50 g of H2O. n(H2O) = 0.387g 18.02 g⋅ mol-1 = 21.48mmol < 68.34mmol
n(H2O) ≈ 50/18 ≈ 2.8 ; n(Na2SO3) ≈ 50/126 ≈ 0.40 All water absorbed is bound as crystal water. Amount of anhydrous
Mg(ClO4 )2 that converts into the hexahydrate:
n(H2O)/n(Na2SO3) ≈ 2.8/0.40 = 7
n(Mg(ClO4 )2 )anhydrous→hydrate = 1 6 ⋅ n(H2O) = 3.58 mmol

Formula of Hydrate: Na 2SO 3 Ÿ7 H 2O m(Mg(ClO4 )2 )anhydrous→hydrate = 3.58 ×10-3mol 223.21g ⋅ mol −1 = 0.799 g
(
%m(hexahydrate) = 0.799 g + 0.387g ) (2.542g + 0.387g ) = 0.4049 = 40.49%
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16
 Formula of a Compound Name of a Compound
Name Derivation Formula Derivation
Some Examples: Some Examples:
AlF 3 aluminum fluoride iron(III) sulfide Fe2S 3
FeO iron(II) oxide iodine trifluoride IF 3
N 2O 3 dinitrogen trioxide barium chloride BaCl2
BaO barium oxide hydrosulfuric acid H 2S
MgCO 3 magnesium carbonate carbon tetrachloride CCl4
CO 2 carbon dioxide potassium oxide K 2O
BCl3 boron trichloride dinitrogen monoxide N 2O
H 2SO 4 sulfuric acid copper(II) oxide CuO
Cu2O copper(I) oxide calcium bicarbonate Ca(HCO 3)2
Ca3(PO 4)2 calcium phosphate magnesium sulfate heptahydrate MgSO 4·7 H 2O
CoCl2·6 H 2O cobalt(II) chloride hexahydrate Epsom Salt

65 66

Organic Compounds Organic Compounds

Essentials Common Hydrocarbons

Hydrocarbons Saturated Compounds that

Methane contain only single bonds:
Compounds that contain “stem”+“ane”
only Hydrogen and Carbon,
as in CnHm
Ethane
Except for a few essential
compounds, prefixes are Halothane
used to indicate the number Propane
of carbon atoms in simple
organic molecules
Ethene (Ethylene) Benzene

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17
 Organic Compounds Trivial Names
Functional Groups
Many fundamental compounds are referred to
Functional Groups: individual atoms or groupings by their own non-systematic name, that is by a
of atoms that are attached to a carbon chain, or to common name, or trivial name.
a ring of carbon atoms, of an organic molecule.
Three important examples:
Give the molecule its characteristic properties.
Compounds might be grouped into classes that Formula Formal Name Trivial Name
contain the same Functional Group. For example
Alcohols: contain the hydroxyl group (–OH) H 2O dihydrogen Water
monoxide
Amines: contain the amino group (–NH2)
NH 3 trihydrogen Ammonia
Carboxylic Acids: the acidic hydrogen is mononitride
contained within a carboxyl group (–COOH) CH 3COOH ethanoic acid Acetic Acid

69 70

Isomers Isomers
Definition Like Composition – Unlike Connection
Isomers: molecules with the same molecular formula, C4 H8 C5H10 NO
but with different chemical structures.

C6H12 C4 H7 F C4 H7 F YES
ring of C
MW = 84.16
string of C
C7H14 C7H14 YES
Isomers display their own characteristic mass spectrum:
Ring String
C8 H6 C8 H8 NO

C5H12O C5H12O NO!

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18
 Isomers and Structural Formulae Key Terms
Structural formulae only show the order in which atoms are
bonded together in a molecule and what types of bonds are anion • alcohol • alkane • binary compound •
present. They do not contain any 3D-information: carboxylic acid •cation • chemical formula •
empirical formula • formula mass • formula unit •
functional group • hydrate • hydrocarbon •
Both formulae inorganic compound • ionic compound • isomer •
have the same molar mass • molecular compound • molecular
connectivity profile: formula • molecular mass • organic compound •
Ball & Stick models illustrate that the two formulae represent different views oxidation state • oxoacid • oxoanion • polyatomic
of the same molecule:
ion • structural formula • ternary compound
Rotate in Space

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