1 CHEM 15.

0 Notes by F5XS Fundamentals of Chemistry

Chemistry is the study of matter (composition, structure and properties), the changes it undergoes, and the energy transformations that accompany those changes. Matter is the stuff that makes up all material things. Energy is the capacity to do work or to produce charge. Technology is the sum total of the processes by which humans modify the materials of nature to better satisfy their needs and wants. Science is the systematically allocated and organized body of knowledge based on experimentation, observation, and careful reasoning. Both of which should be stable, explanatory, and tentative. Interdependence of science and technology  new technology often requires new understanding  new investigations in science require new technology The scientific method is a process that lies at the center of scientific inquiry. 1] definition of the problem 2] data collection/observation 3] formulation of hypothesis and testing 4] evolution into theory after repeated testing Hypothesis  tentative explanation for a set of observations  validity tested by further experiments Natural Law  empirical generalization describing the behavior of nature  may be in the form of a qualitative statement or a mathematical formula A theory is an explanation of observed behavior in terms of a simple model that has familiar properties. A model is a mental image of a phenomenon in terms of something we are familiar with; “makes visible the invisible”. The quality of the investigation and of our resulting understanding of the universe depends on…  the cleverness of the questions asked  the skill with which the experiments are carried out  the skill of the investigator to convert the results of the experiment into an ever more sophisticated understanding of the universe Chemistry/Science is affected by:  budget and profit motives  wars and politics  fads and religious beliefs

2 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Matter  it is the material of the universe  anything that occupies space, has mass and possesses inertia Mass  amount of matter  constant property of a material regardless of location  equivalent to weight of an object at the same location Weight  measure of force with which an object of a given mass is attracted by gravity  varies with elevation or distance from gravitational source Volume is the space occupied by matter.

(Basic) States of Matter  gas – no fixed volume or shape  liquid – distinct volume independent of its container; no specific shape  solid – definite shape and volume Any material under a study may be a homogenous system or a heterogeneous system. A phase is, in a sample of matter, any portion that is homogenous and separated from other part of the sample by a definite surface or boundary. A property is a characteristic that can be noted to describe or identify matter. An extensive property depends on the amount of substance contained while an intensive property does not depend on the amount of substance contained. A physical change is a type of change wherein the sample undergoes a change in physical appearance but not in composition while a chemical change is another type of change wherein the sample is transformed into a chemically different substance. Nuclear change is another type of change wherein the change originates in the nucleus of an atom; the number and identity of the atoms or elements change. A pure substance has a fixed composition while a mixture is a combination of two or more substances in which each substance retains its own chemical identity. An element cannot be broken down into simpler substances by chemical means while a compound is composed of two or more elements united chemically in definite proportions.

Ancient views on matter: Chinese and Greek Philosophers  based on speculation  Chinese book, “Shuching,” claimed that matter is made up of earth, fire, water, metal, and wood

3 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 Empedocles of Greece claimed that matter is made up of fire, earth, water, and air  Leucippus and Democritus described matter as “atomos” (particulate) while Aristotle described matter as “hule” (continuous) John Dalton, 1803, observed through careful experimental observations and measurements that atoms are indivisible, much like a billiard ball, and has mass. This became the first scientific theory of the atom and this was the basis for the billiard ball model of the atom. He was the first to assign specific masses for each atom. Dalton’s postulates  matter is composed of tiny indivisible particles called atoms  all atoms of a given element are identical, but differ from atoms of other elements  compound is composed of the atoms of its elements in a definite fixed numerical ratio  chemical reaction involves the rearranging in atoms in different combinations, the atoms remain intact and do not change  1850’s experiments started to show that atoms possess an inner structure  details on the structure of the atom were made possible due to the advent of …  powerful sources of electrical voltage  studies with gas discharge tubes called “Crooke’s Tube”  discovery of X-rays and radioactivity Crooke’s Tube  glass tube containing gas under low pressure  passing an electric current makes a beam appear to move from the negative end to the positive end  (Joseph J. Thomson’s observation) rays from the cathode travel in a straight line going to the anode  (Joseph J. Thomson’s observation) adding an electric plate on either side of the tube deflects the beams Thomson Model (plum pudding model)  atoms can be subdivided into electrically charged particles with which he called cathode rays  cathode rays travel in a straight line s evidenced by a shadow that forms when an object blocks its path Rutherford’s α-scattering experiment Observation  99% of the α particles went straight through the gold foil  some of the α particles had small angle deflections  big angle deflection by some α particles  a very small percent of the α particles were deflected back

Interpretation  the atom is mostly empty space  attractive encounters with the negative electron  close encounters with a highly positive region  a direct hit at a very small equally massive portion

4 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Characteristics of Rutherford’s nuclear atom  the atom consists of very small, very dense nucleus which is positively charged, containing most of its mass  the atom is mostly empty space and the volume is occupied by the practically a massless electron  the positively charged concentrated in the nucleus is neutralized by the negatively charged electrons moving around the nucleus  the estimated radius of the nucleus is 1/50000 times the radius of the atom Eugene Goldstein’s proton, 1886  used a cathode with holes in a discharged or cathode tube, observed rays passing through the holes in the cathode opposite the direction of the cathode rays  named it as canal rays consisting of positively charged particles with differed in mass and charge depending on the gas inside the tube  1840 times heavier than the electron James Chadwick, 1932, the proton  bombarded a thin sheet of Beryllium with α particles  emission of very high energy radiation similar to γ rays  high energy radiation consisted of electrically neutral particles with mass slightly greater than that of the proton Main features of the Atom  atoms consist of a cloud of negatively charged electrons  the electron cloud occupies most of the volume of the atom  the nucleus consists of protons and neutrons (collectively known as nucleons)  atoms are electrically neutral  the number of protons (and electrons) of one element is different from the number of protons (and electrons) in atoms of any other element  the number of protons in the atom of an element (also the number of electrons) is the atomic number (Z)  mass of an atom is accounted mostly by the nucleons  𝑝 + 𝑛 = 𝐴, which is the mass number  𝐴 = 𝑍 + 𝑛  atoms of the same element which varies in the number of neutrons but have the same number of protons are called isotopes Name Symbol Charge Relative Mass Actual Mass (g) Electron 𝒆− +1 1/1840 9.11 × 10−28 Proton 𝒑+ −1 1 1.67 × 10−24 Neutron 𝒏𝟎 0 1 1.67 × 10−24 𝐴𝑍𝑋 Notation: 𝑨 𝒁𝑿 where 𝐴 is the mass number, 𝑍 is the atomic number, and 𝑋 is the chemical symbol.

Max Planck, 1900  studied the profile of electromagnetic radiation emitted by solids heated to various temperatures  intensity of light emitted by the hot object depends on the energy absorbed/emitted (as gauged by temperature)

5 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 “atoms and molecules could emit or absorb energy only in discrete quantities or bundles”, later called quantum  a quantum is the smallest quantity of energy that can be emitted or absorbed in the form of electromagnetic radiation  energy of a single quantum is equal to a constant multiplied by the frequency of the electromagnetic radiation  𝐸 = 𝑕𝜈 wherein 𝑕 is the Planck’s constant (𝑕 ≅ 6.63 × 10−34 𝐽𝑠) and 𝜈 is the frequency in 𝐻𝑧  energy is always emitted or absorbed in whole number multiples of 𝑕𝜈 Albert Einstein, 1905  used the quantum theory to solve the photoelectric effect  energy is quantized, transformed only in discrete quantities called quanta  electromagnetic radiation, which was thought to exhibit only wave properties, seem to show certain characteristics of particulate matter, which lead to the wave-particle duality of light  experiments important to the elucidation of atomic structure were carried out by physicists Photoelectric Effect  electrons are emitted from the surface of a metal when light strikes it  could not be explained by the wave theory on light  electrons were ejected only when the metal surface was exposed to light of a certain minimum frequency called threshold frequency Electromagnetic radiation is a form of energy transmission through a vacuum or a medium in which electric and magnetic components are propagated as waves.  spectrum – component colors of light or electromagnetic radiation  emission spectrum – either continuous or line spectra of radiation emitted by a substance when heated or passed through a prism  continuous spectrum – emission spectrum of white light or sunlight  line spectrum – emission spectrum of atoms in the gas phase narrow colored lines Niels Bohr, 1913  used the emission spectrum of hydrogen  theory explaining the emission spectrum of the hydrogen atom and suggested an explanation as to why atoms don’t collapse  electrons in the hydrogen atom moves around the nucleus only in certain allowable orbits Bohr’s Model  only allowed energy levels (orbits) are possible for the electron  energy levels are numbered starting with 1 as the first orbit  lowest energy state is the ground state which brings the electron closest to the nucleus Dalton → Thomson → Rutherford → Bohr → Quantum Mechanical Model

6 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Evolution of the Periodic Table 1] Johann Dobereiner – grouping of three elements, triads, with simple physical and chemical properties 2] John Newlands  law of octaves – eighth element starting from a given one is a kind of repetition of the first  arranged the elements in the order if increasing atomic weights 3] Dmitri Ivanovich Mendeleev  produced a table on which the modern classification of elements is based  called it a periodic table, where elements with similar properties are arranged periodically  arranged in the order in increasing atomic masses 4] Julius Lothar Meyer – only a few months after Mendeleev, he published a similar classification of elements 5] Henry Mosely showed that elements can be identified by their atomic number 6] Glenn Seaborg is responsible for bringing down the lanthanide and actinide series in the present Periodic table Periodic Law states that properties of the elements vary periodically with their atomic weights. The modern periodic table  its basic structure and shape is one of the strongest empirical supports for the quantum theory that is used to predict electronic configuration  elements are arranged in the order of increasing atomic number
1 2 13 14 15 16 17 18

3

4

5

6

7

8

9

10 11 12

s block
Lathanide Series Actinide Series

d block Transition Metals

p block

f block Inner Transition Metals  the darker boxes indicate metals while the lighter blocks indicate non-metals; the blocks in between non-metals and metals are the metalloids  horizontal rows pertain to periods while columns pertain to groups

7 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Grp. # Category 6 Atomic number 1 alkali metals 2 alkaline earth metals 13 boron family Chemical symbol 14 carbon family 15 nitrogen family 16 oxygen family 12.01 Atomic mass 17 halogens 18 noble gases The atomic mass is the weighted average of all (natural) isotopic masses of the element.

C

The effective nuclear charge (denoted as 𝑍𝑒𝑓𝑓 ) dictates the trends in the periodic table. A higher effective nuclear charge will yield a stronger attraction of nucleus to the electrons. 𝑍𝑒𝑓𝑓 = 𝑍 − 𝜎 where…  𝑍 is the nuclear charge which is related to attractive force of positively charged nucleus to the negative electrons  𝜎 is the shielding constant, which is related to the number of inner shells shielding the outer shell  usually more dominant than 𝑍 Atomic properties and trends  periodicity of valence  most striking and significant periodic variation among elements in the periodic table  representative elements exhibit this most consistently  valence shell electrons control the chemical properties of an element  periodic variation in the number of valence electrons leads to periodic variation of chemical properties of elements  a “stable element” has energy levels completely filled with valence electrons and are relatively stable and generally unreactive (group 8, noble gases)  atomic size  the atomic radius is half the distance between two nuclei of a diatomic molecule  greatest at the lower left part of the table  ionization energy  energy needed to pull out the outermost electron  related to the tendency of the atom to form cations  greatest at the upper right part of the table  electron affinity  ability to accept one or more electrons  measure of the tightness of binding an additional electron  related to tendency to form cations  greatest at the lower left part of the table, with many exceptions including the noble gases Valence Shell Electron Pair Repulsion (VSEPR)  used in predicting shapes of species that have main group elements as central atom

8 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 electron pairs will be as far apart from each other in three-dimensional space as possible The polarity of a molecule depends on the relative electronegativities of atoms that comprise it and molecule’s geometry. Electronegativity is the capacity to attract electrons by a bonded atom.

Law of Conservation of Mass  demonstrated by Antoine Lavoisier (1743 – 1794), referred to as the Father of Modern Chemistry  established chemistry as a quantitative science  demonstrated by experiments with careful measurements that combustion involves the reaction of a substance with oxygen  when combustion is carried out in a closed container there is no net change in mass Law of Definite Proportions  Joseph Proust, 1799, pointed out that “a compound is a substance to which nature assigns a fixed ratio”  showed that copper carbonate, whether prepared in the lab or obtained from natural sources, contained the same three elements: copper, carbon, and oxygen, and always in the same proportions  a pure chemical substance contains the same elements in the same definite proportion by mass of its elements  the reaction where there are unreacted or excess illustrate the concept of limiting reactant Law of Multiple Proportions  John Dalton predicted a regularity in the weight relations in the case of the same two elements forming two or more different compounds  in different compounds of the same elements, the different masses of one element that combine with a fixed mass of the other element are in the ratio of small whole numbers Chemical Arithmetic  in studying matter, we need to see and be able to count, weigh, and measure exact volumes of substances  we measure samples of elements that would contain their atoms in the specific ratios that are needed  difficult to weigh a single atom because it is very minute  smallest speck of dust that is visible to the eye has 1 × 1016 particles Atomic Mass  assign a value to the mass of one atom of a given element which is called the reference/standard  by international agreement, the reference element chosen was carbon-12 1  1𝑎𝑚𝑢 = mass exactly equal to the mass of 1 C-12 atom 12  the atomic mass unit (𝑎𝑚𝑢) of an element is the average atomic mass of all naturally occurring mixture of a particular element

9 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 if we take the relative mass of one element in any mass unit, this mass will contain the same number of atoms as would be found in the relative mass of some other element in the same units The molecular mass is the sum of the atomic masses of the atoms in a given chemical formula or covalent compounds. The formula mass is the sum of the atomic masses of the atoms in a given chemical formula of either a molecule or a formula unit of an ionic compound. The chemical formula of a substance represents the kind and number of atoms of the respective elements in a molecular or formula unit of a compound. Mole Concept  atoms react in simple whole number ratios  atoms and molecules are too small to be seen much more to be counted  atoms and molecules are counted by relating number to mass  moles are counting units use by chemists  a mole contains the number of carbon-12 atoms contained in 12𝑔 of carbon12, which is equal to 6.02 × 1023 atoms/particles (6.02 × 1023 is the Avogadro’s number) The number of moles of any substance can be measure using this formula: mass (𝑚) 𝑛 = molar mass (𝑀𝑀) Percentage composition states that, by the law of definite compositions/proportions, a compound always has the same elements in the same ratio by mass. In general, percent composition is taken to mean by mass unless otherwise specified. Empirical Formula  simplest formula  chemical formula that shows the…  kinds of atoms/elements  relative number (simplest ratio) of atoms of each element Molecular Formula  simplest formula  chemical formula that shows the…  kinds of atoms/elements  actual number of atoms of each element

Most stable substances do not exist in the atomic form. Some elements exist in the diatomic state. Atoms of different elements combine to form compounds. When atoms combine, they are held together in fixed proportions by forces of attraction called chemical bonds. Chemical changes consist of breaking of old bonds and the formation of new ones. Atoms interact by changing the number of their valence electrons so as to acquire the electronic structure of a noble gas.

10 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Octet Rule – an atom gains, loses, or shares electrons in chemical bonding in such a way as to attain a valence octet. Electron Dot Symbols, a.k.a. Lewis Symbols, is a system devised to keep track of valence electrons in a chemical reaction. There are three types of chemical bonds, namely metallic bonds, ionic bonds, and covalent bonds. Metallic Bond  demonstrated by the sea-of-electrons model, an oversimplified theory of bonding in metals which can explain some of the observed properties of metals  the forces of attraction between the positive ions and the delocalized electrons  in the crystal, the cations occupy fixed positions but the electrons move freely throughout the crystal Ionic Bond  the structural units or particles in the crystal are cations and anions  formula units of ionic compounds do not exist as separate entities Covalent Bond  the bond that holds atoms together in molecules  the bond formed by sharing a pair of electrons  formed from the combination of nonmetallic elements  arises from the attraction of each electron in a shared pair to both of the nuclei involved in the bond  the two electrons spend most of their time somewhere between the two nuclei Valence Bond Theory  a quantum mechanical model to describe the electronic nature of covalent bonds  provides an easily visualized picture of how electron pairs are shared in a covalent bond  covalent bonds are formed by the overlap of atomic orbitals each of which contains one electron of the opposite spin  each of the bonded atoms maintains its own atomic orbitals, but the electorn pair in the overlapping orbitals is shared by most atoms Multiple Covalent Bonds  atoms may attain complete octets by sharing more than one pair of electrons between them  the more bonds bonding the two atoms together, the tighter the atoms are held together The bond length is the distance between the centers of two atoms joined by a covalent bond. The bond length decreases as the number of shared pairs increases.

11 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

A coordinate covalent bond is a covalent bond in which one atom contributes both electrons shared in the bond. The atom that contributed two electrons is called the ligand. Covalent compounds are compounds that contain only covalent bonds. There are two types of covalent compounds:  molecular covalent compounds contain discrete molecular units  network covalent compounds have no molecular units and have an extensive three-dimensional structure There are two types of attractive forces in covalent compounds:  covalent bonds which are forces that hold the atoms together in the molecule  intermolecular forces of attraction which are forces that operate between molecules The bond polarity is a useful concept to describe unequal sharing of electrons in a bond. Nonpolar covalent bonds have equal sharing of the electron pair in a bond. Equal sharing occurs in molecules of diatomic elements or in between identical atoms with identical neighbors. Polar ionic bond occurs when there is unequal sharing of electron pair in a bond. Unequal sharing occurs when either two atoms are dissimilar or two atoms are identical but not identical in surroundings. Electronegativity is the numerical measure of the ability of an atom in a molecule to attract the electrons shared in a bond; the greater an atom’s electronegativity, the greater its ability to attract electrons to itself. This is related to an atom’s electron affinity and ionization energy. This is used to estimate whether a given bond will be nonpolar covalent, polar covalent, or ionic. Electronegativity is the absolute nonpolar covalent 𝛥𝐸𝑁 < 0.5 value of the difference in polar covalent 0.5 < ΔEN < 2.0 electronegativity values of the bonded ionic 2.0 < ΔEN atoms. This can be used to gauge the polarity of the bonding between two atoms. A Lewis structure describes how the electrons are distributed in a molecule or ion. The formal charge reveals the distribution of electrons in the molecule. It also helps in drawing the most plausible Lewis structures. Resonance structures are one of the two or more structures for a single molecule that cannot be described fully without only one Lewis structure. A resonance hybrid is the structure that results from resonance in which the “true” Lewis structure is represented by the combination of two or more resonance structures. The position of electrons of the resonance hybrid, not those of atoms, can be rearranged in different resonance structures. The electron pair geometry is the overall arrangement of electron pairs around the central atom while the molecular geometry (of a molecule/ion) is the arrangement of the atoms in space.

12 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Repulsive forces decrease in the following order: lone pair lone pair bonding pair vs. vs. vs. > > lone pair bonding pair bonding pair repulsion repulsion repulsion A polar molecule is has separate centers of positive and negative charges that produces a dipole, magnitude given by the dipole moment. Charge distribution of the molecule is determined by the polarity of a molecule’s bonds and its geometry.  any diatomic molecule 𝑋-𝑌 in which 𝑋 and 𝑌 have different electronegativities is polar  the polarity of a polyatomic molecule depends on the vector sum of the dipole moments are to each individual bond

Intermolecular Forces of Attraction (IMFA) are attractions between molecules that account for the excitement of the condensed states of matter (liquid and solid). They are primarily responsible for the bulk properties of matter and are much weaker than chemical bonds London Dispersion Forces are weak, short-lived interactions resulting from the motion of electrons in atoms that are present in all substances. They are involved in the creation of instantaneous and induced dipoles. They are named after Fritz London who theoretically explained these forces in 1980. Dipole-dipole forces are forces that act between polar molecules and are about 1% as strong as covalent bonds. They are effective only when polar molecules are very close together. Hydrogen bonding is a special type of dipole-dipole interaction that have attraction between certain molecules greater than can be accounted for by ordinary dipole-dipole interactions. This bond is generally 5-10% as strong as covalent bonds. A common structural feature about hydrogen bonding is that at least one Hydrogen atom is covalently bonded to a highly electronetagive atom, i.e. nitrogen, oxygen, or fluorine, with at least one unshared electron pair. Polarizability is a measure of the ease with which the charge distribution can be distorted by an external magnetic field. In general, heavier atoms or larger molecules tend to have greater polarizabilities which yields stronger London forces. Shape is also an important indicator of magnitude of London forces.        Strong IMFA leads to: high boiling point high heat of vaporization high melting point high heat of fusion high surface tension high viscosity low vapor pressure

13 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

States of Matter  the physical state at which a substance would normally exist depends on the attractive forces between molecules called IMFA Gas particles have no volume, no attraction for each other and in continuous motion, exerting pressure on its container by colliding on the walls. In liquids  moving particles crowd together in small groups  no structure is required  groups of particles move past each other  individual particles can break from their neighbors and join other groups In solids  particles are held in fixed position by strong forces of attraction  particles packed closely together in a rigid structure  particles are not able to move from one position to another  individual particles vibrate in their position

Properties of liquids and solids in general  molecules of liquids and solids are touching each other and cannot be pushed much closer; nearly incompressible  denser than gases  most substances have density of solids greater than that of liquids (important exception is water)  if temperature of liquid is lowered low enough, molecules won’t have sufficient energy to move and can only vibrate  if temperature is lowered very quickly, molecules get stuck in the disordered arrangement of the liquid  if temperature is lowered slowly, molecules have time to arrange themselves in an ordered structure Metals consist of the uncombined metallic elements. A metallic substance is a lattice of ions within a continuous “sea” of delocalized electrons. Metallic bonding is the electrical attraction between the positive ions and the delocalized electrons. Ionic substances include compounds of metals with non-metals and ammonium compounds. Except for the oxides and hydroxides they are called salts. Ionic compounds consist of positive ions and negative ions occupying alternate positions in a regular lattice. Ionic bonding is the electrical attraction between positive and negative ions. Covalent molecular substances include non-metals and most compounds containing only non-metals. they exist in groups of atoms called molecules. Covalent bonding is the electrical attraction between shared electrons and the positive nuclei of adjacent atoms. A single bond is a shared pair of electrons. In a double bond, four electrons are shared. In a triple bond, six electrons are shared. The noble gases exist as atoms. they have similar physical properties to covalent molecular substances.

14 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Covalent network substances include a few non-metal elements, such as carbon and silicon, and a few compounds containing only non-metals, such as silicon carbide and silicon dioxide. Every atom is covalently bound to other atoms in a lattice. Property Melting Point Electrical Conductivity Solid Molten Metallic high Ionic high Covalent Molecular low Coalent Network very high

conducting conducting insoluble unless reactive variable malleable

nonconducting conducting conducting if soluble very hard very brittle

Aqueous Hardness Malleability Substance

nonconducting nonconducting nonconducting and do not react soft brittle

nonconducting nonconducting insoluble very hard brittle

Property  good conductors of electricity and heat  high melting point and boiling point

Metals

 dense  malleable and ductile  lustrous  non-conductors of electricity when solid  conductors of electricity when molten or in aqueous solution

Explanation  delocalized electrons transfer charge and thermal energy  strong metallic bonding extending throughout the lattice  ions tightly packed in the lattice  distortion does not disrupt the metallic bonding  delocalized electrons cause reflection of light  ions firmly bound in the lattice, so no mobile charged particles  ions are free to move  strong ionic bonding extending throughout the lattice  ions strongly bound in the lattice  distortion causes repulsion between ions of like charge

Ionic Substances

 high melting point and boiling point  hard  brittle

15 CHEM 15.0 Notes by F5XS  non-conductors of electricity when solid molten or dissolved in water, unless a reaction occurs with water to produce ions  low melting point and boiling point  soft solids, liquids, or gases  non-conductors of electricity when solid or molten Covalent Network  very high melting points  hard  brittle Fundamentals of Chemistry  the molecules are uncharged and electrons are localized in covalent bonds or on the atoms  weak forces molecules between

Covalent Molecular

 electrons localized in covalent bonds or on the atoms  strong covalent bonding extending throughout the lattice  atoms strongly bound in the lattice  distortion breaks covalent bonds

Liquids  composed of molecules, atoms, or ions  randomly packed n small groups  amount of free space between particles is quite small  the particles are at constant random motion  the particles attract each other Bulk properties of liquids – variations in the physical properties like boiling point, melting point, vapor pressure; arising from the collection of molecules brought about by intermolecular forces of attraction that may or may not be in operation. Vapor Pressure  pressure exerted by a vapor when in equilibrium with its liquid at a given temperature  vaporization is a process in which passage of molecules from the surface of liquids to the vapor or gas phase  dynamic equilibrium occurs when opposing processes are going on at the same time at the same rate Boiling Point  temperature at which vapor pressure of the liquid is equal to the external pressure  heat of vaporization is energy required to vaporize a certain amount of liquid Freezing/Melting Point  temperature at which solid and liquid coexist within the substance  as pressure increases, melting point generally increases with the exception of water  heat of fusion is the energy required to melt a certain solid

16 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Viscosity  liquids flow because molecules or groups of molecules move past each other  strong intermolecular forces of attraction between molecules would make it more difficult for molecules or group of molecules to move past each other  increase in temperature lowers viscosity Surface Tension  force on the surface of the liquid that makes the area of the surface as small as possible  resistance to an increase in surface area  reason why some insects can walk on water  for a given volume of liquid, the sphere has the smallest surface area  brought about by the difference in the forces between molecules at the surface and molecules in the bulk of the liquid Capillary Action  spontaneous rising of liquid in a narrow tube  a consequence of surface tension  raises the surface of H2O in a glass tube having a small more and lowers the surface of Hg in the same tube  due to the relative strengths of cohesive (IMFA) and adhesive forces Specific Heat  the amount of heat needed to raise the temperature of one gram of substance by 1℃  directly related to the strength of IMFA The heat of vaporization is the quantity of heat that must be absorbed if a certain quantity of liquid is vaporized at a constant temperature. The heat of fusion is the amount of energy absorbed by a solid to the point where the molecules holding their bonds together break apart and form a liquid The heat of sublimation is the amount of energy that must be added to a solid at constant pressure in order to turn it directly in to a gas (without passing through the liquid phase). A phase change is a change from one physical state to another accompanied by a change in energy. A heating curve is a plot of temperature versus time where energy is added uniformly and continuously. A cooling curve is similar to a heating curve but energy is removed at a constant rate. A phase diagram is a representation of the conditions (pressure versus time) at which a substance exists in the gas, liquid, and solid state. The critical point is the highest temperature at which a gaseous substance can be liquefied, above which a gaseous substance cannot be liquefied no matter how high the pressure is. Beyond the critical point, the substance would become a supercritical fluid. The triple point is a point on the phase diagram where the solid state, liquid state, and gaseous state are present in the substance.

17 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Gas laws are natural laws governing the physical properties and behavior of gases. Boyle’s Law states that for a fixed amount of gas at a constant temperature, the volume of the gas is inversely proportional to the gas pressure. Charles’ Law states that the volume of a fixed amount of gas at a constant pressure is directly proportional to the absolute temperature. Avogadro’s Law states that equal volumes of different gases compared at the same temperature and pressure contain equal number of molecules; equal number of molecules of different gases compared at the same temperature and pressure occupy equal volumes; at a fixed temperature and pressure, the volume of the gas is directly proportional to the amount of gas The ideal gas equation is the unifying equation that includes all gas variables and combines the constants into 𝑹, the universal gas constant, which is equal 𝐿 ×𝑎𝑡𝑚 1 to 0.0821 . 𝑚𝑜𝑙 ×𝐾 An ideal gas is made up of gas particles that have no volume, no attractions for each other, and in continuous motion, exerting pressure on its container by colliding with the walls. At standard temperature and pressure, the volume occupied by one mole of gas with 6.02 × 1023 molecules/atoms is equal to 22.4𝐿. Dalton’s Law of Partial Pressures  for a mixture of gases in a container, the total pressure exerted is the sum of the pressures that each gas would exert if it were alone  for a mixture of non-reacting gases, the total pressure will be 𝑃𝛴 = 𝑃1 + 𝑃2 + 𝑃3 + ⋯  assuming that each gas behaves ideally, the partial pressures of each gas 𝑛 𝑃 𝑉 could be expressed as in an ideal gas equation: 𝐴 = 𝐴 = 𝐴 𝑛
𝛴 𝑃 𝛴 𝑉𝛴

Non-ideal gas (Real gases)  show behavior deviating from ideal gases  at high pressures, molecules become crowded and repulsive forces among electrons does not allow the volume of the gas to approach zero  at high pressures, compression and crowding allow for IMFA to be effective, therefore pressure of real gases decrease since collision with walls are decreased as a result of IMFA van der Waals equation: 𝑃 + 2 𝑉 − 𝑛𝑏 = 𝑛𝑅𝑇 where 𝑎 and 𝑏 are 𝑉 specific values for particular gases. The ideal gas equation is corrected for the volume of the molecules and for the IMFA effect on pressure. Kinetic Molecular Theory  a gas is composed of very large number of extremely small particles in constant random straight-line motion According to your calculator, 𝑅 ≈ 0.08205745867 For Casio 𝑓𝑥 − 991 𝐸𝑆 scientific calculators, 𝑅 = CONST27 [CONV26] × 1000 𝑛
2 𝑎

18 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 molecules are separated by great distances  molecules collide with one another and with the walls of their container  there are assumed to be no forces between molecules except very briefly during collisions  individual molecules may gain or lose energy as a result of collisions Kinetic Molecular Equation: 𝑃 = 𝑁𝑉𝑚𝑢 3 where 𝑃 denotes pressure, 𝑁 denotes the number of molecules in a volume, 𝑉 denotes volume, 𝑚 denotes the molecular mass, and 𝑢 denotes the average of the squares of the speed of the molecules. Diffusion and Effusion  properties related to kinetic molecular theory  rates at which diffusion and effusion occur directly proportional to molecular speed  diffusion is the migration/intermingling of molecules of different substances as a result of random molecular motion  effusion is the escape of gas molecules from their container through a tiny hole  𝝁𝒓𝒎𝒔 is the root mean square speed which is the square root of the mean of the squares of the speeds of all molecules of the sample Graham’s Law states that the rates of effusion or diffusion of two different gases are inversely proportional to the square root of their molar masses. effusion rate 𝐴 𝜇𝑟𝑚𝑠 𝐴 = = effusion rate 𝐵 𝜇𝑟𝑚𝑠 𝐵 𝑀𝑀 𝐴 𝑀𝑀 𝐴
2

A chemical reaction is a process in which one set of substances called reactants is converted to a new set of substances called products. Signs of a chemical reaction  color change  formation of a solid (precipitate) within a clear liquid  evolution of gas  evolution/absorption of heat Chemical Equation  symbolic representation of a chemical reaction  law of conservation of mass necessitates a balanced chemical equation  stoichiometric coefficients are added or manipulated to balance a chemical equation  to balance chemical equations by inspection, adjust coefficients by trial and error until a balanced condition is found  the formula of the reactant or product must not be altered to balance the equation

19 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Types of Chemical Reactions  combustion is the complete combustion of C, H, and O compounds which produces CO2 and H2O as the only products  decomposition  combination  precipitation (double displacement)  gas-forming reactions  acid-base reactions or neutralization  oxiadation-reduction reactions or RedOx reactions occur when electrons are transferred from one reactant to another Stoichiometric Proportions – when all the reactants are completely and simultaneously consumed in mole ratios dictated by the coefficients in a balanced chemical reaction The limiting reactant is the reactant that is completely used up on a chemical reaction and dictates the amount of product formed. The excess reactant is present in more than the stoichiometric proportion given in a balanced equation.

Rules for determining oxidation number  any atom in its face or elemental state has an oxidation number equal to zero  for monoatomic ions, oxidation umber is equal to the charge of the ion  fluorine, in all its compounds always has an oxidation number of −1  alkali metals, in all their compounds, have an oxidation number of +1  alkaline earth metals, in all their compounds, have an oxidation number of +2  the elements of group 17 (halogens) have an oxidation of −1 in their binary compounds with a metal  oxygen atoms have an oxidation number of −2 in most of its compounds except in:  its compounds with fluorine, oxygen has a positive oxidation number  peroxides (O2 )  the superoxide ion, O2 , it has an oxidation number of − 2  in most of its compounds, except in hydrides, the oxidation number of hydrogen is +1  in hydrides, where hydrogen is in combination with a less electronegative atom, each hydrogen atom has an oxidation number of −1  other compounds of complex ions not covered by the above rules are assigned oxidation number such that the sum of the oxidation numbers of all the atoms in the compound or complex ion is equal to the net charge of the compound or ion Potential (°𝑬)  measure of the tendency of the half reaction to occur  also called voltage or electromotive force Reduction Potential  tendency of the species to gain electrons  the more positive the reduction potential, the greater is its tendency to occur, the stronger the species can act as oxidizing agent
1 2-

20 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Oxidation Potential  tendency of the species to lose electrons  the more positive the oxidation potential, the greater is its tendency to occur, the stronger the species can act as reducing agent Standard Reduction Potential Table  list of oxidizing agents written as reduction half reactions, in the order of increasing strength with their corresponding potentials  determined by comparing with the potential of standard hydrogen electrode, set at standard conditions:  for aqueous solutions, concentration is at 1 molar  for gases, pressure at 1atm and temperature at 25℃ Cell Potential  sum of the potentials of two half reactions  potential of the overall or net reaction  positive overall cell potential for a reaction indicates that the reaction is spontaneous  for any spontaneous reaction, the stronger reducing agent and the stronger oxidizing agent is on the reactant side

Thermochemistry is a branch of chemistry concerned with heat effects accompanying chemical reactions. A system is a part of the universe we choose to study while the surroundings are the parts of the universe with which the system interacts. Types of systems:  an open system is where both energy and matter can be transferred between the system and the surroundings  a closed system is where only energy can be transferred between the system and surroundings but not matter  an isolated system is where neither energy nor matter can be exchanged between the system and the surroundings Energy transfers are often in the form of heat and work. Heat is the energy transferred between a system and its surroundings as a result of temperature differences. Work is produced by an action force through a distance. Energy is the capacity to do work; something that matter has that can make things happen. Kinetic energy is the energy of an object that is moving. 𝐾𝐸 = 𝑚𝑣 2. In solid, liquid, or gas matter:  individual atomic sized-particles are in constant motion, therefore possesses kinetic energy  for any object, the average kinetic energy of its atomic-sized particles is directly proportional to the absolute temperature (in Kelvin) of the object
2

21 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Potential Energy  stored energy due to condition, position, or composition  energy that an object has because it is either attracted to or repelled by some other object When objects that attract each other are pulled apart, their kinetic energy increases. When they move toward each other, their kinetic energy decreases. When objects that repel each other are pushed toward each other, their potential energy increases. When they are moved apart from each other, their potential energy decreases. Law of Conservation of Energy (First Law of Thermodynamics)  energy can neither be created nor destroyed but can only be transformed from one form to another  in an isolated system, there is no energy transfer, therefore, the total energy of the system is constant In almost all chemical reactions there is either absorption or release of energy. Chemical reactions may be classified based on energy of the system:  in an exothermic reaction…  reaction results in evolution of heat  energy of heat flows out of the system  potential energy of the product is less than the potential energy of the reactant  overall potential energy of the system decreases  in an endothermic reaction…  reaction results in absorption of heat  energy of heat flows into of the system  potential energy of the product is greater than the potential energy of the reactant  overall potential energy of the system increases Enthalpy  change in heat content in a chemical reaction  ∆𝐻 or change in enthalpy is measured  it is impossible to measure the actual heat content of any particular substance  only the apparent changes in heat content when reactants are transformed to products is measured Total energy change in a reaction: ∆𝐻𝑟 =
° 𝐻𝑓 products − ° 𝐻𝑓 reactants

° The heat of formation, denoted by 𝐻𝑓 , is the change in enthalpy that accompanies the formation of one mole of compound from its elements in their standard states, i.e. 25℃ at 1atm.

The standard state is the most stable form of the element at conditions 1atm and 25℃. ° The ∆𝐻𝑓 of an element in its standard or most stable form is zero.

22 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

The spontaneity of reactions make processes occur without outside intervention. It may be fast or slow.  ∆𝐻 may indicate of the likelihood of a chemical reaction occurring unassisted (spontaneity of reactions)  in general, exothermic reactions (−∆𝐻) are more likely to occur spontaneously than endothermic reactions (+∆𝐻), though there are some exceptions A characteristic common to all spontaneous processes is an increase in a property called entropy. Entropy, denoted by 𝑆, is the measure of randomness or disorder. Applying it to molecules, 𝑆solid < 𝑆𝑙iquid ≪ 𝑆gas . The second law of thermodynamics (universal entropy) states that in any spontaneous processes, there is always an increase in the entropy of the universe. If 𝑆univ is…  positive, then entropy of the universe increases, and the process is spontaneous in the direction written  negative, then entropy of the universe decreases, and the process is spontaneous in the opposite direction  zero, then the process has no tendency to occur and the system is in equilibrium Disorder  something that brings about disorder is more likely to occur than something that brings about order  close relationship between randomness and statistical probability  laws of chance sometimes hidden by the changes in energy  if energy changes could be ignored or made less important, statistical probability would become the primary driving force for change Enthalpy and Entropy  two factors that determine whether or not a given physical or chemical event will be spontaneous  may work together or act in opposition ∆𝑆 is dependent on temperature, and related by the Gibbs Free Energy Equation, 𝐺 = 𝐻 − 𝑇𝑆, where 𝐺 is the free energy, 𝑆 is the entropy of the system, and 𝑇 is the absolute temperature in Kelvin. At constant temperature, ∆𝐺 = ∆𝐻 − 𝑇∆𝑆. At constant temperature and pressure, a process is spontaneous in the direction in which free energy ∆𝐺 decreases. To predict spontaneity of processes or reactions, use two functions:  ∆𝑆univ applies to all processes; a process is spontaneous if ∆𝑆univ is positive  ∆𝐺 applies only if at constant temperature and pressure  if ∆𝐺 is negative, the reaction is spontaneous as written  if ∆𝐺 is positive, the reaction is spontaneous in reverse  if ∆𝐺 is equal to zero, the reaction is at equilibrium When a reaction is…  exothermic ∆𝐻 < 0

23 CHEM 15.0 Notes by F5XS         Fundamentals of Chemistry

∆𝑆 > 0 accompanied by an increase in entropy ∆𝐺 will always be negative regardless of the value of the absolute temperature change will occur spontaneously at all temperatures ∆𝐻 > 0 endothermic ∆𝑆 < 0 accompanied by an increase in entropy ∆𝐺 will always be positive regardless of the value of the absolute temperature change will always be non-spontaneous at all temperatures when ∆𝐻 and ∆𝑆 have the same signs, the temperature becomes critical ∆𝐻 > 0  spontaneous only temperatures  not spontaneous temperatures ∆𝐻 < 0  spontaneous at temperatures  spontaneous only at temperatures

∆𝑆 > 0 ∆𝑆 < 0

at at

high all

all low

Implications to the second law of thermodynamics with respect to the present problems of:  environmental pollution  pollution is the scattering of undesirable substances throughout the environment  a direct result of our efforts to create an orderly world  accompanied by an increase in entropy  pollution can never really be eliminated  energy crisis  there is really no lack of energy  problems arise from the unavailability of energy  in our day-to-day life, we do not consume energy; we merely convert it from a usable form to an unusable form  more correctly, the search for energy is a search for usable forms of energy:  stored in the bonds of chemical fuels  in nuclear fuels  provided by sun’s rays

Chemical Kinetics is the study of rates of chemical reactions, rate laws, and reaction mechanism. Collision Theory (Arrhenius Theory) states that for a chemical reaction to occur:  reacting particles must collide effectively to enable outer shell electrons to interact  collision must be with enough force to overcome the repulsive forces between electrons surrounding the nuclei of the atoms  collision of particles must be in the correct orientation  atoms and electrons rearrange, bonds are broken and new bonds are formed in the production of new substances during collision Factors affecting rates of reaction:  nature of reacting substances depend on specific bonds involved; a more stable molecule has a lower rate of reacting

24 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 concentration of the reactants – rates increase with higher concentration of reactant; more molecules yield more frequent collisions  state of subdivision of the reactant – rates increase with a higher surface area  presence of a catalyst – catalyst decreases the activation energy, consequently hastening the rate of reaction  temperature – generally, a high temperature increases the rates of reaction Solubility is the maximum amount of substance that dissolves in a given quantity of solvent at a given temperature to form a saturated solution. Before the formation of a solution, both solute and solvent have an ∆H > 0. After the formation of the solution, the resulting ∆H < 0. Also, ∆Hsolution = ∆H1 + ∆H2 + ⋯ + ∆Hn Factors affecting solubility:  nature of solute and solvent – only substances with similar polarity will dissolve each other  pressure – a high pressure will increase the solubility of gases in liquids  temperature  a higher temperature will have a decrease in the solubility of gases in liquids  a higher temperature will have a higher rate of solution of solids  a higher temperature will increase the solubility of most solids in liquids Factors affecting rate of dissolution:  stirring (agitation) will increase frequency of interaction between solvent and solute particles  state of subdivision or particle size of solute – a finely divided solute has large surface area, allowing more contact surface with solvent molecules  temperature – increasing the temperature increases the average kinetic energy of solute and solvent particles, therefore increasing frequency of interactions Quantitative was of expressing concentration:  solutions provide a fluid medium that allows particles to collide and react  quantitative measurements of reactants and products in a reaction in solution is made possible through stoichiometry  it is performed to be able to express quantities of solutes in reactions Expressions of concentration in solutions as ratios:  molar concentration or molarity n  denoted by M = solute where volume is expressed in liters  the unit of molarity is molar, denoted by M  this expression of concentration is usually used in determining mole quantities of reactants and products  molal concentration or molality n  denoted by b = solute 2 where mass is expressed in kilograms  the unit of molality is molal, denoted by m
2

V

m solvent

The symbol for molality is interchangeable between b and m. It is replaced by b in this case to disambiguate the symbol for molality and mass.

25 CHEM 15.0 Notes by F5XS  molar fraction n  denoted by 𝑥 = substance  𝑥1 + 𝑥2 + ⋯ + 𝑥𝑛 = 1  percent concentration m  %w/w = solute  %v/v =
m solution V solute n

Fundamentals of Chemistry

 %w/v =

V solution m solute V solution

 parts per million (ppm) and parts per billion (ppb) mg  ppm%w/w = solute ppm%w/v = ppm%w/v =  ppb%w/w = ppb%w/v =
kg solution mg solute L solution μ g solute mL solution μ g solute kg solution μ g solute L solution

Stock solutions are solutions that have high concentration and are prepared in the laboratory. Working solutions are dilute solutions prepared from stock solutions. To make dilute solutions from concentrated solutions, use the formula 𝐶1 𝑉1 = 𝐶2 𝑉2 . Stoichiometry of reactants in solutions:  calculations performed are similar to pure substances taking part in a reaction  the only difference is that after finding the number of moles needed, the volume containing these number of moles is calculated  stoichiometric coefficients provide key in calculating the quantities of chemicals involved in the reaction Colligative properties of aqueous solutions:  physical properties of solution different from the solvent  dependent on the relative amounts of the components  more dilute solutions approach properties of solvent o vapor pressure lowering o vapor pressure of solution is lower than that of pure solvent o as the concentration of solute increases, the decrease of the vapor pressure difference between pure solvent and solution increases o Raoult’s Law describes vapor pressure lowering in an equation: 𝑃Σ = ∗ ∗ χA PA + χB PB o boiling point elevation o consequence of vapor pressure lowering o boiling point of solution is higher than that of the pure solvent o ∆𝑇𝑏 = 𝐾𝑏 𝑚 where ∆𝑇𝑏 is the boiling point elevation, 𝐾𝑏 is the boiling point elevation constant of water (0.52℃/𝑚), and 𝑚 is the molality of the solution o freezing point depression o freezing point of solution is lower than that of solvent o physically may be explained by the inability of the solvent molecules to arrange into the open structure of its solid form due to obstruction caused by solute molecules at its usual freezing temperature

26 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

o a much lower temperature is needed to further compress the solvent molecules together and for the hydrogen bonding to take effect among the solvent molecules o ∆𝑇𝑓 = 𝐾𝑓 𝑚 where ∆𝑇𝑓 is the freezing point depression, 𝐾𝑓 is the freezing point elevation constant of water (1.86℃/𝑚), and 𝑚 is the molality of the solution o osmotic pressure o pressure exerted in a solution to hold off or stop osmosis o osmosis is process which particles in solution selectively move through a semi-permeable membrane

Chemical Equilibrium  initially, reactants present at definite concentrations  as reaction proceeds, concentrations of reactants decreases; those of products increase  after a time, concentrations level off and become constant, undergoing a state of chemical equilibrium Characteristic features of systems at equilibrium:  the system does not gain matter from the surroundings nor lose matter to the surroundings, which means the equilibrium system is a closed system  the system is dynamic, i.e. the opposite processes occur at the same time  measureable properties of the system remain constant, i.e. the opposite processes occur at the same rate  at a given temperature, the extent to which reactions occur before equilibrium is attained can be indicated by a constant related to the concentrations of reacting substance Reverse reactions are reactions where conditions allowing the reactants to form the products also permit the products to reform the reactions. Irreversible reactions are reactions where products cannot give back the reactants under the given conditions. Equilibrium Changes:  chemical equilibrium represents a balance between forward and reverse reactions  changes in experimental conditions may disturb the balance  shift the position of equilibrium so that more or less of the desired product is formed Le Chatelier’s Principle (1885)  “when a stress is applied to a system in equilibrium a chemical change occurs in the direction that relieves the stress and brings the system to equilibrium again” – Henry Louis Le Chatelier  suggests an outcome  offers no explanation on the effect of changes  does not produce numerical values Equilibrium changes may involve any of the following:  changing the concentration of a reactant or product

27 CHEM 15.0 Notes by F5XS  changing the pressure of gaseous systems  changing the temperature Changing the concentration of a reactant or product:  if a system is at equilibrium and the concentration of a reactant is increased so that the system is no longer at equilibrium, more reaction will occur in the direction that reduces the concentration of that reactant Changing the pressure of gaseous systems:  the simplest way to analyze the effects of a volume change on an equilibrium system is to count the number of molecules of gaseous substances on both sides of the equation  an increase in pressure, or decrease in volume, always drives the reaction in the direction of the fewest number of molecules of gas  reaction involving liquids or solids have no way of counteracting pressure changes  addition of inert gas to a system in equilibrium will have no effect on the position of equilibrium; individual concentrations and partial pressures of reacting gases remain unchanged Changing the temperature: to predict the effect of temperature change…  treat heat as a reactant (in an endothermic change) or as a product (in an exothermic change)  predict the direction of shift as if an actual reactant or product is added or removed Law of Mass Action (1864)  proposed by the Norwegian chemists Cato Maximilian Guldberg and Peter Waage  expresses the relationships between the concentrations of reactants and products at equilibrium in any reaction  describes equilibrium condition in a reaction: aA + bB → cC + dD Equilibrium Constant  numerical value obtained when actual equilibrium concentrations are substituted into the equilibrium constant expression  value of 𝐾𝑐 depends on what the reaction is, how the reaction is written, and temperature 𝑐 𝑑  𝐾 = 𝐶 𝐷 𝐴 𝑎 𝐵 𝑏 A large equilibrium constant favors the products strongly and the reaction goes essentially to completion. A small equilibrium constant favors the reactants strongly and the reaction proceeds hardly at all toward completion. An equilibrium constant equal to or near 1 is at equilibrium, when quantities of reactants and products are comparable. A homogeneous equilibrium is an equilibrium in which the reaction species are in the same phase while a heterogeneous equilibrium is an equilibrium in which the reaction species are in different phases. Fundamentals of Chemistry

28 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Rules for writing equilibrium constant expressions  the unit of concentration usually used for species in condensed phases are in mol and for those in gaseous phases, either mol or atm is used  concentrations of pure solids, pure liquids (in heterogeneous equilibria) and solvents (in homogeneous equilibria) do not appear in the equilibrium constant expression  the equilibrium constant is treated as a dimensionless quantity  in quoting a value for the equilibrium constant, the balanced equation and the temperature must be specified  when the equation for a reversible reaction is written in the opposite direction, the equilibrium constant is the reciprocal of the original equilibrium constant In calculating for the value of the equilibrium constant: −1  𝐾𝑒𝑞 of reverse reaction is 𝐾𝑒𝑞  multiplying the coefficients of balanced equation by a factor, 𝑛, means that the original equilibrium constant is raised to the 𝑛th power The 𝐾𝑐 is an expression of 𝐾𝑒𝑞 in concentration while the 𝐾𝑝 is the expression of 𝐾𝑒𝑞 in pressure, calculated as 𝐾𝑝 = 𝐾𝑐 𝑅𝑇∆𝑛𝑔𝑎𝑠 .

Arrhenius definition of acids and bases:  first proposed in 1884 and is the oldest, most restrictive and simplest definition  an Arrhenius acid is a neutral molecule that dissolves in water to give H+ ions and an anion and it increases the H+ of water  an Arrhenius base is a neutral molecule that dissociates in water to give OH− ions and a cation and it increases the OH − of water  an acid-base reaction in the Arrhenius sense is the coming together of H+ and OH− to form water resulting in the neutralization of the acid and the base  acid + base → salt + water Brønsted-Lowry definition of acids and bases:  suggested independently by Brønsted and Lowry in 1923 and is more general than the Arrhenius definition  a Brønsted-Lowry acid is a substance that donates a proton  a Brønsted-Lowry base is a substance that accepts a proton  acid + base → conj. acid + conj. base As to whether it is the forward or backward reaction that is going to be favored depends upon the relative strengths of the pairs of reacting cid and base. The strength of an acid depends upon its tendency to give up a proton, while the strength of a base depends on its tendency to accept a proton. The dissociation constant in water is frequently used as a measure of the relative strengths of acids and bases. Strong acids and bases are those that almost completely ionize in water with 𝐾𝑎 > 2. For a strong acid, the only acid present in the solution is H3 O+. The only base present in solutions of a strong base is OH− Weak acids and bases have their equilibria toward the left. These have small acidity constants and basicity constants, respectively.

29 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

Lewis definition of acids and bases:  proposed by Lewis in 1923 and it is the broadest definition and includes all other definitions  a Lewis acid is a substance that accepts an electron pair and it must have a vacant orbital which it can use to form a covalent bond with the electron pair of the base; examples:  molecules with an atom having less than an octet of electrons  molecules in which the central atom has available d orbitals and may acquire more than an octet of electrons  molecules with multiple bonds between atoms of dissimilar electronegativity  cations  a Lewis base is a substance that donates an electron pair and must have an available electron pair; examples:  molecules with an atom having an unshared electron pair(s)  anions  any reaction that leads to the formation of a coordinate covalent bond is a Lewis acid-base reaction A buffer is a solution that is able to absorb small additions of concentrated acids and bases without giving rise to a significant change in the pH of the solution.

Nuclear Chemistry  study of nuclear reactions and their uses in chemistry  deals with changes in matter originating in the nucleus of an atom  involves changes in the atomic number and/or mass number of the reactant Radioactivity is the spontaneous disintegration of an unstable atomic nucleus with accompanying emission of radiation in order to form a more stable species. A nuclide is a nucleus with a specified mass number, A; number of protons, Z; and number of neutrons. Isotopes are atoms of the same element where the nuclei contain different number of neutrons. A nucleon is a particle that makes up the nucleus, i.e. the protons and the neutrons. Nuclear Particle Alpha (Helium) Beta− (electron) Beta+ (positron) Neutron Proton Gamma Symbol
4 4 2 He or 2 α 0 0 −1 β or −1 e 0 0 1 β or 1 e 1 0n 1 1 1 p or 1 H 0 γ or γ 0

Nuclear Binding Energy  energy released in a nuclear fission or fusion reaction  this energy is very large and can be harnessed positively (nuclear power plants) or destructively (atom bomb or H-bomb)  dependent on the mass defect which is highest observed in bismuth

30 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 nuclear stability is dependent on the neutron:proton ratio Characteristic of the Nuclear Binding Energy:  greater than electromagnetic and gravitational forces  short range and effective only at very short distance Nuclear Stability depends on:  ratio of neutrons to protons (belt of stability)  concept of complete nuclear shell or closed shell configuration (magic numbers)  odd-even number of nucleons (an even number is more stable) The belt of stability is a general guide to the area within which all stable nuclei are found. Odd-even combination and nuclear stability proton neutron number of stable nuclides even even 163 even odd 55 odd odd 50 odd even 4 Magic Numbers proton neutron 2 2 8 8 20 20 28 28 50 50 82 82 114 126 184

Types of nuclear reactions:  alpha decay  usually emitted by heavy nuclei  as nuclei becomes larger, protons increase, proton-proton repulsion becomes larger, and the nuclear binding force becomes insufficient to hold all protons together  tend to reduce nucleons to become stable by emitting an α particle, similar to a He nuclide A −4 4  A Z X → Z −2J + 2 He  beta decay (electron emission)  usually occurs when neutrons are in excess, then they are transformed into protons with an emission of β−  electrons are produced as a nuclear reaction occurs 1 1  1 0 n → 1 H + −1 e  beta decay (positron emission)  usually occurs when neutrons are in excess, then they are transformed into protons with an emission of β+  positrons are produced as a nuclear reaction occurs 1 0  1 1p → 0n + 1e  electron capture or 𝐊-capture  usually happens when protons are in excess  nuclear stability is achieved by capturing one of the inner electrons converting a proton to a neutron  energy in the form of x-rays are emitted because outer electrons in the higher energy levels fill up the vacant lower energy level left by the captured electrons 1 1  1 1 p + −1 e → 0 n + γ

31 CHEM 15.0 Notes by F5XS Fundamentals of Chemistry

 gamma emission  high energy photons or radiation similar to x-rays but shorter wavelength, high frequency, and high penetration  no mass so the A and Z of nucleus remain unchanged  energy changes that accompanies almost all other radioactive emissions although not represented in nuclear reactions Nuclear Fission  heavy nucleus splits into two or more lighter nuclei  occurs when heavy nuclei are struck with projectiles or bullets Nuclear Fusion  nuclei of light elements are made to combine to form heavier nuclei  fusion reaction takes place only at very high temperatures called ignition temperatures which can be supplied y an atom bomb  more energetic than fission reaction but difficult to harness

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