Fundamentals of Inorganic Chemistry (ChemIO!!): Lecture Note, (2-14-2015 Review Activi ies 1, The rotatable structure opposite shows the ZnS (zine blende) structure in which the Zn’ ion is surrounded by 4 S” ions. The distance from the centre of the tetrahedron to the comer, d, is: d= ~ and anion-cation-anion bond angle, @ = 109.5° as shown in the diagram below. Fig.2.15 Calculate the radius ratio and predict the CN and geometry of zinc blende structure. 2. Outline the similarities and differences between cubic and hexagonal close-packed arrangements of spheres, paying particular attention to (a) coordination numbers, (b) interstitial holes and (c) unit cells. 3. State the coordination number of a sphere in each of the following arrangements: (a) cop; (b) hep; (c) bee; (d) fee; (e) simple cubic. 4, (@) Lithium metal undergoes a phase change at 80K (1 bar pressure) from the a- to b- form; one form is bee and the other is a close-packed lattice. Suggest, with reasons, which form is which, What name is given to this type of structural change? (b) Suggest why tin buttons on nineteenth-century military uniforms crumbled in exceptionally cold winters. Unit Three Acid-Base Theories and the Solvent System 3.1 Introduction sour" or "tart," si The word "acid" comes from the Latin word acidus, meaning water solutions of acids have a sour or tart taste. Lemons, grapefruit, and limes taste sour because they contain citric acid and ascorbic acid (vitamin C) By, Bezabih Kelta(MSe. Inorg Chem) l6~ Department of Chemistry, Wolaita Sodo UniversityFundamentals of Inorganic Chemistry (ChemIO!!): Lecture Note, (2-14-2015 * Common properties of acids include: acids produce hydrogen gas when reacted with active metals like Na, K, Mg, Zn etc., change color of indicators (litmus paper is red in acids), they have sour taste, neutralize bases and form salt and water, etc. ‘* Bases are chemical opposite of acids. 3.2 Definitions of Acid and Base Different researchers defined acids and bases in different perspectives. 1 Arrhenius Acids and Bases In the Arrhenius acid-base definition, acids and bases are classified in terms of their formulas and their behavior in water: * An Arrhenius acid is a substance that has H in its formula and when added to water increases the concentration of H” ions present. + An Arrhenius base is a substance that has OH in its formula and when added to water increases the concentration of OH’ ions present. Ho Illustrations : HC(g) ———> _ H"(aq) + CI(aq) #0 NaOH(aq) ———+_ Na (aq) + OH (aq) Some typical Arrhenius acids are HCI, HNOs, and HCN, and some typical bases are NaOH, KOH, and Ba(OH)>. © Thus the acids inerease the H’ ion and bases increase OH” ion concentration when dissolved in it The H” ion produced by an Arrhenius acid is always associated with a water molecule to form the hydronium ion, H30* (aq). Limitations to the Arrhenius Theory 1) The theory defined an acid or a base in terms hydrogen or hydroxyl compounds only. However, this does not explain the weak base ammonia (NH3), (that does not contain OIF itself}, which in the presence of water, releases hydroxide ions into solution. Bo Dissociate : NH; ———*—+NH,OH ———— NH,’ + OH 2) It offered no satisfactory explanation for the acid property of various substances such as AICI, NH,NO, ete. By: Bezabih Kelia(MSc. Inorg. Chem) -17- Department af Chemistry, Wolaita Sodo UniversityFundamentals of Inorganic Chemistry (ChemiO!!): Lecture Note, (2-14-2015 3) A bare proton cannot exist in solution. 4) The theory does not include non-aqueous solvents. 3.2.2 Bronsted-Lowry Acids —Bases Theory In the Lowry-Bronsted definition:- © Anacid:- is a hydrogen ion(arefen}onor; © A base: - is a hydrogen ion (proton) acceptor. The transfer of a proton to a proton acceptor is an acid-base reaction under the Lowry-Bronsted definition. A general equation expressing proton transfer in aqueous solutions is: AH(ag) + Bag) A’(aq)+ BH'(aq) Acid base Example: acid HC! H H #H ff ae H—C—O-H —> H—C—O-H + CE =—9 ; H H base base Acid-Conjugate base and Base-conjugate acid pairs According to Lowry and Bronsted, when acid reacts with a base, there are two conjugate acid- base pairs ie., for every acid there exists a base which is produced when the acid loses its proton and for every base there exists an acid which is produced when the base accepts proton, D4An acid is one proton (hydrogen ion, H") than its conjugate base and a base is one proton less than its conjugate acid. AH@q) + Blag) — At@q) + BHaq) Acid] Base2 basel Acid 2 In the above illustration, acid 1 and basel are conjugate pairs and, similarly, acid 2 and base 2 are conjugate pairs. Example: NHs(aq) + H:SO«(aq) NHs"(aq) + HSO¥(aq) Basel Acid 2 Acid 1 Base2, By, Bezabih Kelia(WSe. Inorg. Chem) 18> Department of Chemistry, Wolaita Sodo UniversityFundamentals of Inorganic Chemistry (ChemiO!1): Lecture Note, (2-14-2015 Thus, in the above example, H2SO, and HSO, are acid-base conjugate pair; and NH," and NH; are acid- base conjugate pairs. Note: A strong acid always has a weak conjugate base. A weak acid always has a strong conjugate base. ‘Activity 3.1 1. Write at least three -base conjugate pair reactions. 2. Write: a) Conjugate acids for the bases: CO", NHs, HzO, OH’, SO,” and H2PO, b) Conjugate bases for acids: HPO,*,H2O, HCI, CHsCOOH, H30",HSNHs and HsPOs. 3. Label each acid-base conjugate bair in the following reaction H30"(I) + Fag), DH (aq) + HFlaq) 3.2.3 Lewis definition of Acids and Bases According to this theory: » A : an electron pair acceptor. > Base: an electron pair donor. It turns out that it may be more accurate to say that "Lewis acids" are substances which are electron-deficient (or low electron density) known as electrophiles and "Lewis bases” are substances which are electron-rich (or high electron density) - known as nucleophiles. Several categories of substances can be considered Lewis acids > positive ions; > having less than a full octet in the valence shell; > polar double bonds (one end); > expandable valence shells. Several categories of substances can be considered Lewis bases: > negative ions; > one of more unshared pairs in the valence shell; v polar double bonds (the other end); > the presence ofa double bond. ‘The product of any Lewis acid-base reaction is called an adduet, a single species that contains a new covalent bond: By, Bezabih Kelia(MSe. Inorg. Chem) 8- Department of Chemistry, Wolaita Sodo UniversityFundamentals of Inorganic Chemistry (ChemiO!1): Lecture Note, (2-14-2015 3. 4 Solvent System Definition of Acids and Bases According to the solvent system definitions > A solute that causes an increase in the concentration of the solvonium ions (positive ions) and a decrease in the concentration of solvate ions of solvent (negative ions) is defined as an acid. > A solute that causes an increase in the concentration of the solvate ions and a decrease in the concentration of the solvonium ions of solvent is defined as a base. Example: In liquid ammonia, KNH; (supplying NH2 ~) is a strong base, and NH4NOs (supplying NHL’) is a strong acid. In liquid sulfur dioxide (S02), thionyl compounds (supplying 02+) behave as acids, and sulfites (supplying SO;*” behave as bases. > The solvents which contain hydrogen and from which proton can be derived are known as protic solvents, e.g. water, liquid ammonia and hydrogen fluoride. Solvents which have no tendency to accept or release protons are known as aprotic solvents, e.g. benzene, chloroform, CCla, ete. Review Activity 3 1. Discuss briefly the advantages of Arrhenius definition of acids and bases. List at least 3 limitations of Arrhenius definition of acids and bases. Al Arrhenius acids are also Bronsted-Lowry acids and vice versa (True/False). BwN If the pH of a solution is 9.55 at 25°C, what is the hydroxide-ion concentration in the By: Bezabih Kelta(MSc. org. Chem) -Z0- Department of Chemistry, Wolaita Soda University