Chem 1020 - Chapt. 1 - Chemical Foundations

Chem-1020: General Chemistry-I(B)
Chapter 1: Chemical Foundations

Key Words:
 Scientific Method
 Models of Atomic Structure (via scientific method)
Question to be addressed: How was the most fundamental concept in

chemistry, i.e., atomic structure, established via scientific method ?
Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Chem-1020: General Chemistry-I(B)
Chapter 1: Chemical Foundations

 Key Concepts:
1. Scientific method and Chemistry mindset;
2. Three fundamental chemical laws  Experimental foundations for the first atomic model;
3. Evolution of the “ATOMIC” concept: Five models for atomic structure;
4. Modern view of atomic structure.
 Reading Assignment: Z&Z: Chapter 1: pp. 28 ~ 50.

 Questions/Exercises Assignment: Z&Z: pp. 50, 51, 51a~51f.
 For Review: pp. 50 ~ 51.
 Review Questions: 1 ~ 8;
 Questions: 11, 13, 15, 17, 19, 21, 23;
 Exercises: 25, 27, 29, 31, 33, 35; 37, 39, 43, 45, 49, 51; 53, 55, 57, 59.
* “Z&Z” refers to our adopted textbook by Steph S. Zumdahl and Susan A. Zumdahl, 2nd Ed., 2016
1. Scientific method and Chemistry mindset
 Basic Steps in Scientific Method: the process of scientific inquiry.
Measurement !
 Observation: quantitative and qualitative

 Hypothesis: explanation (interpretation) of observation
 Experiment: test and validation of hypothesis
The key !!
law  Law: summary & abstraction of general observations
 Theory (Model): a human invention attempting to

explain and interpret observed phenomena (a set of
tested and validated hypotheses).
 Every law has its limitation!

 Every theory has its limitation!
The key !!

In Scientific Method, “experiments” hold the key:
 To make observations and measurement, we rely on experiments;
 To test and validate a hypothesis, we rely on experiments;
 To propose a law, we rely on abstraction of the general observations from experiments;
 To examine a theory’s validity and limitation, we rely on experiments;
Experiments provide us with the means to obtain all the facts and evidences
for laws, hypotheses, and theories.

In the study of chemistry, always bear in mind the

implications and limitations of three key terms:
 Law;
 Theory (or Model);
 Experimental Observations (Individual Facts).

Chemistry
started to become
a scientific endeavor and scientific discipline
only when the scientific method was practiced in
 the study of matter and their changes,
 the establishment of atomic structures.

Chemistry: what is it all about ?

 At macroscopic level, chemistry is science of matter, concerned about their
composition, structure, properties, change, and energetics associated with change.
 At microscopic level, chemistry is science of atoms and molecules, concerned

about their composition, structure, interactions, properties, change, and energetics
associated with change.
 Chemistry also aims at gaining an understanding of the connection(s) between

the macroscopic world (“visible to our eyes”) that we experience in our daily life
and the microscopic world(“invisible to our eyes”) of molecules and atoms.
 Scientific method we just described applies to the study of chemistry. Of

particular significance is to learn how to think and reason at both macroscopic
and microscopic levels, and on the basis of the experimental observations.

Chemistry: an overview (of Chem-1020)
Since matter is composed of atoms, our understanding of matter inevitably
depends on our understanding of
 Atoms  their structures and properties.
(Chapts. 1, 2)
 Bonding  the formation of molecules/substances and their properties.
(Chapts. 3, 4)
 Changes  quantitative aspects of chemical change: mass conservation.
(Chapts. 5)
 Changes  quantitative aspects of chemical change: energy conservation.
(Chapt. 7)
 Changes  types of changes: transfer of “something”, such as H+, e-, ions…
(Chapt. 6)
 Substances  assemblies of molecules (or atoms and ions); their structures,
(Chapts. 8, 9) properties and inter-conversions.

But before we start discussing specific topics in chemistry,

let’s have some mindset preparation  how to think like a chemist ?
(i) Length scale in chemistry (Key word: Structure)
(ii) Energy scale in chemistry (Key word: Interaction)
(iii) Time scale in chemistry (Key word: Change)
(iv) Thinking at multi-scales and from multi-facets

Think like a chemist: the mindset preparation for the study of chemistry 10 m
(i) Length scale in chemistry (Key word: Structure)
10
Matter (macroscopic structure > 10-3m)
Molecules (microscopic structure ~ 10-7 ~ 10-9 m)
Atoms
H, (microscopic
C, O, Fe, Cu, Ag,
Cl,….Na,structure Au…..
at ~ 10 -10 m)
( Relevant terms: length, size, shape, structure, assembly, …) 10-10 m

Think like a chemist: the mindset preparation for the study of chemistry
(ii) Energy scale in chemistry (Key Word: Interaction or force)
100 ~ 101 kJ.mol-1
molecule molecule
( non-bonding interaction )
( and weak interaction )
Energy Energy L 102 ~ 103 kJ.mol-1
HO O+ Energy
atom atom
2+ 2
HO H H ( bonding interaction )
L
L ≥ 1015 kJ.mol-1
Energy nucleus nucleus

( nuclear interaction )
( Relevant terms: bond, force, interaction, energy, … )

Think like a chemist : the mindset preparation for the study of chemistry
(iii) Time scale in chemistry (Key Word: Change)
t1/2 ~ 5730 yrs

H
~ 7 fs
ultra-fast ultra-slow
10-15 s 1015 s
femtosecond petasecond
32 mil. yrs !
(Relevant terms: time, rate, kinetics, dynamics, transition state, … )

Think like a chemist: the mindset preparation for the study of chemistry :
(iv) Thinking at multi-scales and from multi-facets of a substance (or a molecule)
- Key words: structure + interaction + change + …….
Length scale Macroscopic
( structure ) observations
Substance
interpretation
implication
( property )
Time scale
( change ) Microscopic
origins
Energy scale
( interaction )
Note: Important dimensions when studying chemistry.

2. Three Fundamental Chemical Laws
Three fundamental chemical laws:

 Law of conservation of mass ( 1785, Antoine Lavoisier, French )
 Law of definite proportions (of mass) ( 1806, Joseph Proust, French )
 Law of multiple proportions (of mass) ( 1808, John Dalton, English )
These three laws are fundamental because they formed the basis for the
idea of “atom” and their stoichiometry in compounds and in reactions.
Chapters 1 & 2 Chapters 5 & 6

 Law of conservation of mass ( Lavoisier’s law, ~1785 ):
Statement: Mass is neither created nor destroyed.
( in either physical or chemical changes.)
𝟏
Example: HgO (s)  Hg (l) + 𝟐 O2 (g)
Implication: A substance may undergo various changes, but

the total mass must be always accounted for. Antoine Lavoisier
(1743 – 1794, French)
Significance: This law is one of the foundation stones for chemistry. It made possible
for the quantitative studies of the transformations of substances,
therefore for the discovery of elements and new substances, by
examining the mass (weight).

 Law of definite proportion (Proust’s law, 1806):

Statement: A given compound always contains exactly
the same proportion of elements by mass.
.
Example: For CO2, regardless its amount, where it
appears and how it appears, the ratio
mc : mo = 1 : 2.67, always;
Joseph L. Proust
Implication: Elements combine in a specific mass ratio (1754 –1826, French )
when they form a compound.
Significance: It pointed to the mass as the first characteristic property of

“elemental particles” (elements) in substances.
Note: This law does not apply to “non-stoichiometric compounds”(known as berthollides, as opposed to the
stoichiometric compounds or daltonides ) !
 Law of multiple proportions (Dalton’s law, 1808):

Statement: When two elements form a series of compounds,
the ratios of the masses of the second element
that combine with 1 gram of the first element
can always be reduced to small whole numbers.
Example:
N2O
John Dalton
(1766 – 1844, English)
NO
NO2
Implication: A given “elemental particle” has a definite mass, and different

type of “elemental particles” have different masses.
In compounds, elements combine with each other in the integer
multiples of the “elemental masses”.
Question: N2O3 and N2O5 are also two compounds containing N and O elements only. Check if they fit into the
table above. And your rationale ?
All three fundamental chemical laws point to

one property of “elements”:
(atomic) mass !
Indeed, “atomic mass” was the first property once thought
to be unique to each type of element, and therefore, was used
to “differentiate” between elements.*
This property(atomic mass) can be studied by one of the

simplest scientific measurements, weighing!
* Of course, we now know that “atomic mass” is NOT the unique property to differentiate between elements
because of the existence of isotopes.
Put together, three fundamental chemical laws,

 Mass is conserved (for any changes) (Lavoisier, 1785);
 Mass in Definite proportions (in a given compound) (Proust, 1806);
 Mass in Multiple proportions (between different compounds) (Dalton, 1808).
These three laws suggest the existence of some fundamental “elementary

particles”(atoms), each with a “characteristic” mass, that combine with each
other according to certain stoichiometry(ratio in whole numbers or integer numbers).
Indeed, these three laws form the foundation for the first atomic theory
based on scientific method: the Dalton’s atomic theory.

3. Five Models for Atomic Structure
The foundation stones of chemistry are

atoms.
This section highlight the milestones in the establishment of
the modern view of atoms.
When studying this section, please note that
(1) the progressive and evolutional nature of our view of atoms, and
(2) each atomic model has its own key experimental foundation, and
(3) every “newer” atomic model was built on the basis of the older model(s)
plus some “newer” experimental observation(s), and
(4) the newest (the modern view of) atomic model, the quantum mechanical
model of atomic structure, is the one that can account for most (but still not
all) of the experimental observations so far.

(i) Dalton’s atomic theory (1808):

« A New System of Chemical Philosophy »
Based on the observations in three fundamental chemical laws
that “elemental particles” have characteristic “masses”, Dalton
proposed that

 Each element is made up of tiny particle called atoms;

 Atoms cannot be created, subdivided or destroyed; John Dalton
( 1766 – 1844, English )

 All atoms of the same element are identical (in mass);
Different elements have different types of atoms (different masses);

 Compounds are formed from atoms of the constituent elements; A given
compound always has the same relative number and types of atoms;

 Chemical reactions occur when atoms in substances are re-arranged and/or re-
combined; Atoms themselves are not changed in a chemical reaction.

(i) Dalton’s atomic theory (1808): continues……

The 1st
Dalton’s atomic model (“billiard model”): Model !
 Atoms are ‘billiard’-like, structure-less, undividable
‘balls’ with uniform mass. Each type of atoms has a
characteristic mass.
John Dalton
r ( 1766 – 1844, English )
Experimental foundation for Dalton’s atomic model:

 Three fundamental chemical laws.
 The property on which Dalton’s model was proposed: atomic mass

Dalton’s atomic theory is the first atomic model established via scientific
method, and is based on the premise that the atoms of different elements could be
distinguished by differences in their weights (masses).*
Dalton’s atomic theory could nicely explain three fundamental chemical
laws observed at that time. Some of its main ideas survived till today except those
statements relevant to the nature and (inner) structure of atoms.
Dalton’s atomic theory did not allow for the unambiguous determination of
molecular formulas, nor was it successful in helping determine relative atomic
masses, largely because speculative assumptions(often wrong) have to be made.
Dalton’s atomic theory, only when supplemented with the Gay-Lussac’s Law of
combining volumes and Avogadro’s hypothesis, allowed for the accurate
determination of formulas of certain gases and the masses of certain atoms at
the dawn of chemistry(as a scientific discipline).
* We now know that this is not entirely accurate because of the existence of isotopes!
Law of combining volumes (Gay-Lussac, 1809):
Statement : The ratio between the volumes of the reactant
gases and the products can be expressed in
simple whole numbers (under the same T and p ! ). Joseph Louis Gay-Lussac
( 1778 – 1850, French )
Examples : Gay-Lussac’s experiment
Mtotal unchanged
H2 O2 H2O
1V 2V Vtotal changed
2V
H2 HCl Mtotal unchanged
Cl2
1V 1V 2V Vtotal unchanged
Implication: For a chemical process, Mtotal is conserved, but not necessarily the Vtotal.
What is then the Vtotal proportional to? One possibility, which is consistent
with the 3 fundamental laws and the Dalton atomic theory, is that the Vtotal is
proportional to the total number of gas particles (Ntotal) which MAY be
changed together with the mass of individual gas particles(gas molecules)
in the reaction.
Avogadro’s hypothesis (1811):
Statement : At the same T and P, equal volumes of different
gases contain the same number of gas particles.*
Examples : Under Avogadro’s hypothesis, Gay-Lussac’s Amedeo Avogadro
experiment can be rationalized as ( 1776 - 1856, Italian )
Nparticle changed
mparticle changed
Vtotal changed
Mtotal unchanged!
2 molecules of hydrogen react with 1 molecule of oxygen  2 molecules of water
Nparticle unchanged
mparticle changed
Vtotal unchanged
1 molecule of hydrogen reacts with 1 molecule of chlorine  2 molecules of hydrogen chloride Mtotal unchanged!
Implication: The gas volume is proportional to the total number of particles at a

given T and p, regardless of the individual gas particle’s mass.
* For the time being, let’s think the term ‘molecule’ as a particle containing certain number of atoms.
Note: Avogadro himself did NOT measure nor knew what was now called the Avogadro’s number !

Gay-Lussac’s Law of combining volumes and Avogadro’s hypothesis are
consistent with the notions of Dalton’s atomic theory, namely
 the existence of smallest particles (i.e., atoms) characterized by their masses;

(different types of “particles” have different masses).
 in a chemical change, the total number of these “smallest particles”(i.e., the
total number of atoms) are unchanged (or conserved!).
 these particles (i.e., atoms) combine with each other in definite proportion
(for a given compound) and multiple proportions (for different compounds);
 the masses of these particles(i.e., atoms), as well as masses of their
combination in compounds, can be measured.

Dalton’s atomic theory (as well as the Gay-Lussac’s Law of combining volumes
and Avogadro’s hypothesis) was unable to address several important questions:
 What is an atom made of ? (Dalton was completely wrong on this point!)

 How do the atoms of the various elements differ? (only in mass or else?)
 How do the atoms combine with each other? and what is the underlying
principle that dictates their combination and re-organization in a chemical
reaction?
 ……
To address these questions, we need to learn the inner structure of atoms, by
making more experimental measurements and observations that may shed light
on the inner composition of atoms!!

Key experimental evidences for the inner-composition and structure of atoms :

 The existence of sub-atomic particles: Radioactivity(a particles/He2+, 1897)
 The existence of electron in atoms: Thomson experiment(1903) and Millikan experiment(1909)
 The existence of atomic nucleus: Rutherford experiment(1911)
 The quantization of electron energy in atoms: H atomic spectrum and Bohr model(1913)
 The existence of proton(s) in atomic nucleus: Another Rutherford experiments(1919)
 The existence of neutron(s) in atomic nucleus: Chadwick experiment(1932)

 The existence of heavier sub-atomic particles: Radioactivity (1896)
Radioactivity = Radioactive decay = Radioactive emission :
 Serendipitously discovered the a emission from Uranium(U) salt;
(now we know that a particle = He2+ , but not then!)
 Significance: It suggests that atoms are not structure-less and

un-dividable mass-balls as proposed in Dalton’s atomic model,
and are made of even smaller particles.
Antoine Henri Becquerel
 Although it was recognized that a emission was originated from 1852 –1908, French
Nobel Prize in Phys, 1903
atoms, there was no knowledge whatsoever then about the inner
structure of atom and how the observed radioactive
emission is related to the atomic structure.
 We now know that three common types of radioactive
decays from the nucleus of atoms (named by Rutherford ) :
 a decay generates a emission of a particles: He2+ ions
 b decay generates b emission of b particles: electrons
 g decay generates g emission of g particles: electromagnetic wave. Marie Curie Pierre Curie
1867–1934, French-Polish 1859 –1906, French
Nobel Prize in Phys. 1903 Nobel Prize in Phys. 1903
Nobel Prize in Chem. 1911 (piezoelectricity)
Discovered polonium (Po) and radium (Ra)
(ii) The existence of electron in atom and Thomson’s atomic model (1903):
Thomson’s cathode-ray tube experiment:
(+)
(-)
(-)
(+)
(+)
(-) Joseph John Thomson

1856 –1940, British
Nobel Prize in Phys. 1906
On the basis of the cathode-ray tube experiment, Thomson
 Postulated the existence of negatively-charged particles (now called electrons ) in atoms;
𝒆
 Determined the charge-to-mass ratio of an electron : = -1.76 x 108 C/g
𝒎𝒆
 Suggested that atom must also contain positively-charged component that balance exactly
the negative charge carried by electrons;

(ii) The existence of electron in atoms and Thomson’s atomic model (1903)
The 2nd Model !
Thomson’s atomic model (or plum-pudding model, 1903) :
 Atoms are made of negative and positive particles, and

the negatively charged electrons are randomly distributed
in a positively charged sphere. The mass of an atom is still
evenly distributed!
r Joseph John Thomson

1856 –1940, British
Experimental foundation for the Thomson’s atomic model :

 Thomson’s cathode-ray tube experiment.
 The property on which Thomson’s model was proposed: Existence of electrons in atom.

 The property of electron: Millikan experiment (1909)
 Performed experiments involving the charged oil drops;
 Determined the magnitude of the charge on a single electron;
e = 1.592 × 10−19 coulomb (Modern value: e =1.602 x 10−19 C )
 Calculated the mass of the electron ( from e/me ratio of Thomson);
me = 9.04 x 10−31 kg (Modern value: me = 9.109 ×10−31 kg )
Robert A. Millikan
1868 – 1953, American
Oil-drop experiment: Nobel Prize in Phys 1923
 measured the force on tiny charged droplets of oil suspended against
gravity between two metal electrodes; Knowing the electric field, the
charge on the droplet could be determined.
 Repeating the experiment for many droplets, the results could be

explained as integer multiples of a common value (1.592 × 10−19 C),
the charge on a single electron.
Note: One of the nice application of the oil-drop experiment is to accurately measure the Avogadro’s number.

(iii) The existence of atomic nucleus and Rutherford’s nuclear model ( 1911 )
 Rutherford Experiment: to test Thomson’s plum-pudding-model of
atom, he used the a particles (He 2+) to bombard thin Au metal foil.
Ernest Rutherford
1871 –1937, NZ-born British
 Rutherford Experiment: the observation is inconsistent with the Nobel Prize in Chem 1908
Thomson’s plum-pudding-model of atom.
Au film
beam of
a particles What is the IMPLICATION
of the observations from
Rutherford experiment ?
Rutherford experiment Expectation from Observation from

“the plum-pudding model” Rutherford experiment
(iii) The existence of atomic nucleus and Rutherford’s nuclear model ( 1911 )
 Rutherford Experiment: the implications?
The mass of an atom is NOT evenly distributed on its size! Rather, it is
condensed into a VERY small volume “within atom” called nucleus!
Imagine what would happen when a particles hit Au atoms:

M(a ) = 4 Da
M(Au) = 197 Da
𝒎𝒂 𝟒
𝒎𝑨𝒖
= 𝟏𝟗𝟕 = 0.02 bounce back if they hit on nuclei!
Ernest Rutherford
𝒎𝒂 1871 –1937, NZ-born British
= 7300 pass through if they hit on electrons! Nobel Prize in Chem 1908
𝒎𝒆
As an analogy, let’s look at a metal shotput vs. a plastic ping-pong ball:

Bounce back !
𝒎𝒔𝒉𝒐𝒕𝒑𝒖𝒕 𝟕𝟐𝟓𝟕 𝒈 a particle vs. Au nucleus = ping-pong vs. shotput
= = 2688
𝒎𝒑𝒊𝒏𝒈𝒑𝒐𝒏𝒈 𝟐.𝟕 𝒈 Pass through!
a particle vs. electrons = shotput vs. ping-pong

(iii) The existence of atomic nucleus and Rutherford’s nuclear atom model ( 1911 )….continues
The 3rd
Rutherford’s Model (nuclear atom model): Model !
  Atom has a dense and tiny center of positive charge

called the nucleus that carries most of atom’s mass;
  Electrons travel randomly around the nucleus at a

relatively large distance.
nucleus (dense and small)
Electron (diffuse and ‘large’) Ernest Rutherford

1871 –1937, NZ-born British
Nobel Prize in Chem. 1908
Experimental foundation for Rutherford’s nuclear atom model :

 Rutherford’s a-particle scattering experiment.
 The property on which Rutherford’s model was proposed: Existence of atomic nucleus.
(The mass of an atom is NOT uniformly distributed ! Rather, it is concentrated in
a VERY VERY tiny space within the atom.)

(iv ) The quantization of electron energy in atoms and the Bohr’s atomic model (1913)
 Experimental observations: H atomic absorption and emission spectra
Coulomb's law :
prism 𝟏 𝒒𝟏𝒒𝟐
detector Ee =
𝟒𝝅𝜺𝟎 𝒓
H2 prism detector
H2 gas
H2
prism
Rutherford’s atomic model
H2 gas
 If Coulomb’s law applies, Ee would be continuous since r is continuously changeable!
 However, inconsistent with the Rutherford’s atomic model and Coulomb’s law, it was
observed that H atoms take(or absorb) and release (or emit) energy in specific quantities
(quantized), not in any arbitrary amount (NOT continuously changeable) !

(iv ) The quantization of electron energy in atoms and the Bohr’s atomic model (1913)
Bohr’s atomic model (Shell model or Planetary model , 1913) : The 4th Model !
  A small positively charged nucleus surrounded by electrons that

travel in circular orbits (called shells) around the nucleus — similar
in structure to the solar or planetary system.
  The essence of this model is the quantization of electron’s motion

and its associated energy.
atom
absorbs light
Niels Bohr
atom (1885 –1962, Danish)
emits light
Nobel Prize in Phys 1922
Experimental foundation for the Bohr’s atomic model (1913):

 H atom’s absorption and emission spectra (and the other atomic spectra);
 The property on which Bohr’s model was proposed: the quantization of electron energy in H atom.

 Let’s Summarize: 4 atomic structure models so far
(please pay attention to the experimental basis and observation(in red) for each model ! )
3rd. nucleus
1st. 2nd. 4th.
-
+ -
-
electron
Dalton’s model Thomson’s model Rutherford’s model Bohr’s model
 “billiard-ball” model  “plum-pudding” model  “nuclear” model  “shell” model
 3 Fundamental laws  cathode-ray-tube expt.  a -particle scattering expt.  H spectra
 atomic mass  electron  nucleus  quantization of “e” energy
 Each model is valid only to “certain” experimental observations (partial truth)!

 Each newer model can account for all the earlier experimental observations!
 Observation(s) still not accounted for then and the questions arisen:
Observation: Radioactivity (He2+, e-, and EM wave can be emitted from nucleus!).
Question: Was the atomic nucleus undividable or else? the composition of nucleus?
Other observations: H-spectra fine structure, spectra of multi-e atoms, periodicity, …

(v) Post-Bohr model observations: the composition of atomic nucleus
(a) Discovery of proton in atomic nucleus.
(Another Rutherford experiment, 1919).
 Bombardment of nitrogen gas by a(He 2+) particles,

14N + α → 17O + p
(the first reported nuclear reaction).
 mp = 1.6726 ×10−27 kg, Rutherford (right)

𝒎𝒑 and his assistant Hans Geiger
 ≈ 1,836,
𝒎𝒆
 q = + 1e = 1.602 ×10−19 C
 The word “proton” was coined in 1920.

(v) Post-Bohr model observations: the composition of atomic nucleus
(b) Discovery of neutron in atomic nucleus.
(Chadwick experiment, 1932).
 mn = 1.6749 ×10−27 kg (as a comparison, m p = 1.6726 ×10−27 kg)

𝒎𝒏 𝒎𝒏
 ≈ 1,839, ≈ 1.001…
𝒎𝒆 𝒎𝒑
 qn = 0
 The word “neutron” was coined by his teacher Rutherford. James Chadwick
1891 – 1974, English
How was the mass of neutron determined ?

(1) Nuclear scattering experiment: 𝟏𝟏
𝟓𝐁 + a ( 𝟒𝟐𝐇𝐞)  𝟏𝟒𝟕𝐍 + n
(2) Energy conservation;
(3) Chadwick’s value: mn = 938  1.8 MeV;
(comparing with the current value mn = 939.57 MeV.
(4) Conversion to kg: E = mC 2
Let’s Summarize: Post-Dalton’s model observations  the inner-composition of atoms
Neutron
Nucleus &
Electron Proton Student
of
Student
of
Chadwick
e- energy quantization
The modern view:
Thomson Rutherford Student Quantum Mechanical
of
Model
( Bohr and many others )
Bohr
2nd model 3rd model 4th model 5th model

(vi) Quantum Mechanical Model of Atomic Structure:
 The modern view of atomic structure (Chapt. 2 for details)
 At chemistry level, the modern view (or the quantum mechanical model) of
atomic structure contains four essential components: (a) the composition of
atom, (b) the inner organization of atom, (c) the behavior of electrons in atom,
and (d) quantum mechanical theory that explains the behavior of electrons in
atoms.
 The first three components, i.e., the composition of atom, the inner
organization of atom, and the behavior of electrons in atom are entirely based
on the experimental observations (the key experimental observations that we have
previously mentioned in this chapter and many more).
 The Quantum Mechanical Theory, which was built on several postulates, was
established to account for the observed electron behaviors in atoms(and
molecules etc.).
In the next, we outline the important features of the quantum mechanical model
of atomic structure. Its detail description will be discussed in Chapter-2.
3. Five Models for Atomic Structure The 5th Model !
(vi) Quantum Mechanical Model of Atomic Structure : 𝒓𝒏𝒖𝒄𝒍
≈ 10-5
The modern view of atomic structure (Chapt. 2 for details) 𝒓𝒂𝒕𝒐𝒎
𝑽𝒏𝒖𝒄𝒍
 Atom consists of a tiny nucleus and electrons that move around it. ≈ 10-15
𝑽𝒂𝒕𝒐𝒎
 Nucleus consists of protons and neutrons, called nucleons.
 Proton has a positive charge equal in magnitude to electron’s
negative charge. The number of proton in a nucleus is equal to
the number of electrons in atom, and is called atomic number
( ~ 1 fm )
of the atom. Atomic number specifies the uniqueness of an atom.
 Neutron has virtually same mass as proton but no charge.
 Atoms with same number of protons (i.e., same number of electrons) ( ~ 0.1 nm or ~ 1 Å )
but different number of neutrons are called isotopes and
belong to the same element. The total number of protons
and neutrons is called the mass number of the atom.
 Electrons in atoms moves in “orbitals” with fixed energy,
and their behaviors are governed by Quantum Mechanics.
 The chemistry of an atom arises from its electrons, especially
electrons in its outer-most shell (with highest energy!). 𝒎𝒏𝒖𝒄𝒍 𝒎
𝒎𝒆
≈ 1836 ~ 1839; 𝒎𝒏 ≈ 1.001…
𝒑

(vi) Quantum Mechanical Model of Atomic Structure: (see Chapt. 2 for details)
thinking and imagining in two extremes: extremely small and extremely large; .
100 m : 1 mm
 About “nucleus” :
𝒓𝒏𝒖𝒄𝒍
 extremely small size, ~ 1 fm (10-15 m); ≈ 10-5
𝒓𝒂𝒕𝒐𝒎
 extremely large density, ~ 1012 kg/cm3 (~ billion tons/cm3 !)
 About “electrons” : dOs = ~ 22.6 g/cm3 !

 extremely fast moving speed; dearth-core = ~ 13 g/cm3 !
 motion and energy are quantized;
 About “atom” :
 the mass of an atom is very uneven and is dominantly in its tiny nucleus;
 the size of an atom is determined by the space occupied by its electrons, and is quite “empty”;
 Number of protons (atomic number = No. electrons) dictates the uniqueness of atom;
 The electrons, especially the outmost or the most-energetic ones, not the nucleus, dictates
the chemical behaviors of atoms.
 About “isotopes” :
 isotopes of a given element differ in the numbers of “neutrons” contained in their nuclei,
therefore in atomic masses. Isotopes have the same number of electrons and show (almost)
identical chemical properties. Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST
𝒓𝒏𝒖𝒄𝒍
Let’s imagine a physical picture about an atom: 𝒓𝒂𝒕𝒐𝒎
≈ 10-5
Now, imagining that you hold an atom in your hand, and 𝑽𝒏𝒖𝒄𝒍
𝑽𝒂𝒕𝒐𝒎
≈ 10-15
 Its MASS is dominantly in a
extre……mely DENSE and
extre……mely SMALL space  nucleus (+).
 Its SIZE is dominantly dictated by

extre…..mely DIFFUSE and
extre……mely SOFT space electrons(-).
 BLURRED boundary !
 Effectively EMPTINESS !
Warning! In this picture, the sizes of

“atom” and its “nucleus” are not in
proportion! If the size of the nucleus is
as shown, the size of the atom would
be ~10x bigger than Lecture-Theater-C!
1 mm : 100 m  10-5 !!!
KEY MESSAGES:
 None of the atomic models is perfect, including our “modern view” of
atoms (Quantum mechanical model), which will be detailed in Chapter-2 !
 Each atomic model has its MERITS (which we still use today!) and LIMITATIONS
(which we have already abandoned in newer models ). Some of the experimental observations
about atoms still can not be explained even with the quantum mechanical
model, the newest and the most modern view of atomic structure!
 Each newer atomic model was built on the basis of the previous model(s),
as well as the newer experimental observations available at the time when it
was proposed !
 We will learn and stay with the “Quantum Mechanical Model of Atomic
Structure” (so-called “the modern view”) since it is the model that can
account for most(but still not all) of the experimental observations so far,
especially, how electrons are arranged in atoms ?

Chapter-1 : Key concepts checklist
Key concepts checklist :

 Basic steps and procedure of scientific method.
 Chemistry: what is it all about ?
 Three fundamental chemical laws  Experimental foundations for the first atomic model.
 Five atomic models and their major experimental foundations.

( Merits and limitations of each model )
 The main components of the modern view (Quantum mechanical model) of atomic structure.
Many important questions remain unanswered by far:

 How are the electrons in an atom arranged (i.e., the electronic structure of an atom)?
 More generally, how are atomic structures related to their chemical behaviors(e.g., bonding,
reactivity, stability, periodicity……)?
 ……
These questions will be addressed by Quantum Mechanical Model of Atomic Structures

in Chapter-2!
Chem 1020: General Chemistry IB
END

Chem 1020 - Chapt. 1 - Chemical Foundations

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Chem 1020 - Chapt. 1 - Chemical Foundations

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Chem-1020: General Chemistry-I(B)

Chapter 1: Chemical Foundations

Question to be addressed: How was the most fundamental concept in

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Chapter 1: Chemical Foundations

 Reading Assignment: Z&Z: Chapter 1: pp. 28 ~ 50.

 Observation: quantitative and qualitative

law  Law: summary & abstraction of general observations

 Theory (Model): a human invention attempting to

 Every law has its limitation!

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 To test and validate a hypothesis, we rely on experiments;

 To propose a law, we rely on abstraction of the general observations from experiments;

 To examine a theory’s validity and limitation, we rely on experiments;

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

In the study of chemistry, always bear in mind the

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Chemistry: what is it all about ?

 At microscopic level, chemistry is science of atoms and molecules, concerned

 Chemistry also aims at gaining an understanding of the connection(s) between

 Scientific method we just described applies to the study of chemistry. Of

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

But before we start discussing specific topics in chemistry,

(ii) Energy scale in chemistry (Key word: Interaction)

(iii) Time scale in chemistry (Key word: Change)

(iv) Thinking at multi-scales and from multi-facets

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Matter (macroscopic structure > 10-3m)

Molecules (microscopic structure ~ 10-7 ~ 10-9 m)

( Relevant terms: length, size, shape, structure, assembly, …) 10-10 m

Energy Energy L 102 ~ 103 kJ.mol-1

Energy nucleus nucleus

( Relevant terms: bond, force, interaction, energy, … )

t1/2 ~ 5730 yrs

(Relevant terms: time, rate, kinetics, dynamics, transition state, … )

Note: Important dimensions when studying chemistry.

Three fundamental chemical laws:

 Law of definite proportions (of mass) ( 1806, Joseph Proust, French )

 Law of multiple proportions (of mass) ( 1808, John Dalton, English )

Chapters 1 & 2 Chapters 5 & 6

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Implication: A substance may undergo various changes, but

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

 Law of definite proportion (Proust’s law, 1806):

Significance: It pointed to the mass as the first characteristic property of

 Law of multiple proportions (Dalton’s law, 1808):

Implication: A given “elemental particle” has a definite mass, and different

All three fundamental chemical laws point to

This property(atomic mass) can be studied by one of the

Put together, three fundamental chemical laws,

These three laws suggest the existence of some fundamental “elementary

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

The foundation stones of chemistry are

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

(i) Dalton’s atomic theory (1808):

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

(i) Dalton’s atomic theory (1808): continues……

r ( 1766 – 1844, English )

Experimental foundation for Dalton’s atomic model:

Prof. Xiao-Yuan Li, Dept. of Chemistry, HKUST

Implication: The gas volume is proportional to the total number of particles at a

(i) Dalton’s atomic theory (1808): continues……