Advanced Inorganic Chemistry Study with Dr. Jumaeri & Dr. F. Widhi Mahatmanti

1. KIMIA ANORGANIK LANJUT Dr. Jumaeri, M.Si/ Dr. F. Widhi Mahatmanti Pendidikan IPA S2 Program Pasca Sarjana UniversitasNegeri Semarang

2. IDENTITAS MATA KULIAH • NAMA MATA KULIAH : KIMIA ANORGANIK LANJUT • CAPAIAN PEMBELAJARAN LULUSAN CP Pengetahuan: Menguasai ilmudasar lain yang menunjang pemahaman ilmu kimia dan keterkaitannya sesuai dengan perkembangan iptek. • CAPAIAN PEMBELAJARAN MATA KULIAH Memahamisecaraseksama, telitidancermatdanmengertisecarakomprehensifdanbertanggungjawabtentangprinsip-prinsipreaksikimiaanorganikdan faktor-faktor yang mempengaruhi, kestabilantermodinamikadankinetikadalamreaksianorganik, teorikoordinasi (teori ikatan kovalen, teori medan kristal dan teori orbaital molekul)danprinsip-prinsipreaksikoordinasi, kinetikadanadsorpsipadat-cairdalamkaitannyadenganpenangananlimbahindustrimenggunakanadsorben/katalisberbasiskonservasi. • DOSEN PENGAMPU : Dr. Jumaeri, M.Si/ Dr. F. Widhi Mahatmanti, S.Si., M.Si

3. DAFTAR MATERI

4. CHEMICAL REACTIONis the focal point of any chemical studies

5. Why do chemical reactions occur?The purpose of this chapter is to examine the nature of chemical change. Focusing on the recognizing all setting forth the basic principles that help us to understand whychemical reactions occur. For the very essence of practical chemistry is the scientific control of chemical change.

6. If it is known why it occurs, then wecan know what conditions are necessary to cause or prevent its occurrence, and wecan direct our ingenuity toward establishing such conditions. Furthermore, such understanding should be invaluable to students, who without it are faced with an almost infinite variety of chemical equations to be memorized but with 110 basis for recognizing that they do make sense.

7. Before we can consider "Why" reactions occur, it is necessary to think of what happens during the occurring of a chemical reaction.Reactants  productsIn order for this to happen, atoms, which are initially attached to one another in a certain way in the reactants, become separated, at least to some extent, and rearranged in the products.

8. h E1 = mgh1 E2 = mgh2

9. q heat SYSTEM THE CONCEPT OF ENERGY Definition Energy could be defined as the capacity of a system to do work

10. The First Law of Thermodynamics : In ordinary processes, energy is conserved, it is neither created nor destroyed q heat W SYSTEM work

11. If heatq is added to a system and work w is done by the system, the total amount of energy added to the system, (q - w); is not destroyed but is stored within the system to increase the internal energy ∆U q heat W SYSTEM ∆U work

12. THE INTERNAL ENERGY ∆U = q - w

13. ∆U : How to measure? Considering that mechanical work w is equal to p∆V : ∆U = q - p ∆V ∆U = qv measurable at constant volume

14. Since most chemical processes proceed at constant pressure rather than at constant volume, it is more convenient to use other new definition of internal energy called enthalpy : H = U + pV or ∆H = ∆U + p∆V ∆U+ p ∆V = qp ∆H = qp measurable at constant presure

15. If enthalpy (or internal energy) is the driving force of chemical processes, it is reasonable to expect that all chemical processes should be followed by a heat release (exothermic). • In practice, however, although it is true that most chemical processes are exothermic, some endothermic (heat absorbed) chemical processes do exist. • It may be concluded, therefore, that enthalpy (or internal energy) is NOT the driving force of chemical processes

16. The Second Law of Thermodynamics : It is impossible to take heat from a body of uniform temperature and convert it entirely into work without causing a change in the thermodynamic state of some other body. It is impossible to have chemical processes, working with a 100 % efficiency. Some waste energy must also be released.

17. THE CONCEPT OF FREE ENERGY ∆G = ∆H - T∆S Free energy Waste Energy Enthalpy

18. ∆G = ∆H - T∆S Chemical Bonding System Structure

19. + A B A B CHEMICAL BONDING : A Thermodynamic Interpretation

20. ATRACTIVE ENERGY : • Between nucleus A and electron B • Between electron A and nucleus B Uatt= - Catt/r • REPULSIVE ENERGY : • Between nucleus A and nucleus B • Between electron A and electron B Urep= +Crep/r

21. U r Urep= + Crep/r Uatt= - Catt/r

22. BOND ENERGY : The energy required to break down chemical bond into separate atoms BOND LENGTH : The equilibrium distance between two atoms involving chemical bond.

23. BOND ENERGY vs INTERAL ENERGY INTERNAL ENERGY U : The most stable chemical bond would be formed at the lowest internal energy BOND ENERGY: The stronger chemical bond would be formed with bigger bond energy

24. Chemical processes tend to proceed spontaneously in the direction of diminished free energy, i.e. when the free energy change, G, is negative. ∆G is the driving force of chemical processes

25. Chemical processes tends to proceed spontaneously only under one of the following sets of conditions : • If the total bonding forces in the products exceed those in the reactants and the total disorder (entropy) of the products is higher; or • If the total bonding forces in the products exceed those in the reactants and the total disorder in the products is lower but not enough lower to make TS greater than H; or • the total bonding forces in the products are weaker than those in the reactants but the entropy increase (increase in disorder) is more than large enough to compensate for the heat absorbed.

26. GA > GB GA = GB GA < GB ΔG< 0 ΔG= 0 ΔG> 0 Spontaneous change : A  B A  B is at the equilibrium state Spontaneous change : B  A A  B

27. CHEMICAL EQUILIBRIUM : A Thermodynamic Interpretation Gi = Gio + RT ln [i] A  B ∆G = GB – GA GB GA

28. GB = GBo + RT ln [B] GA = GAo + RT ln [A] ∆G = ∆Go+ RT ln [B]/[A] A  B ∆G = ∆Go+ RT ln Q Q : reaction quotient

29. A  B At equilibrium state (∆G = 0) : - ΔGo= RT ln K THEORETICAL CONCEPT K= [B]eq/[A]eq PRACTICAL APPLICATION

30. a A + b B c C + d D A general chemical process : K = [C]c[D]d/[A]a[B]b

31. A. Electrolytic Dissociation of Water H2O  H+ + OH- Kw = [H+] [OH-]

32. Ion Product of Water Kw :

33. B. Equilibrium of Acids and Bases : HA  H3O+ + A- Ka = [H+] x [A-]/[A] B + H+ BH+ + OH- Kb = [BH+] x [OH-]/[B]

34. Acidity and Bacisity Constant :

35. Kais the experimental measure of acid strength Kbis the experimental measure of base strength

36. THE PRINCIPLES OF ENTROPY

37. P, V, T P, V, T

38. MORE ORDRED LESS DISORDRED LOW ENTROPY LESS ORDERED MORE DISORDERED HIGH ENTROPY 

39. STRONG CHEMICAL BONDS LARGE BOND ENERGY LOW INTERNAL ENERGY LOW ENTHALPY ~ ~  WEAK CHEMICAL BONDS WEAK BOND ENERGY HIGH INTERNAL ENERGY HIGH ENTHALPY ~ ~ 

40. ∆G = ∆H - T∆S System Structure Chemical Bonding

41. Principle-1 : Chemical processes tend to proceed spontaneously in the direction of diminished free energy, i.e. when the free energy change, G, is negative. ∆G = ∆H - T∆Sis the driving force of chemical processes

42. Chemical processes tends to proceed spontaneously only under one of the following sets of conditions : • If the total bonding forces in the products exceed those in the reactants and the total disorder (entropy) of the products is higher; or • If the total bonding forces in the products exceed those in the reactants and the total disorder in the products is lower but not enough lower to make TS greater than H; or • If the total bonding forces in the products are weaker than those in the reactants but the entropy increase (increase in disorder) is more than large enough to compensate for the heat absorbed.

43. ∆G = ∆H - T∆S System Structure Chemical Bonding

44. Chemical processes tends to proceed spontaneously,if the total bonding forces in the products exceed those in the reactants and the total disorder (entropy) of the products is higher ∆H = (HP-HR) < 0 ∆G = ∆H - T∆S ∆G < 0 ∆S = (SP-SR) > 0

45. Chemical processes tends to proceed spontaneously, If the total bonding forces in the products exceed those in the reactants and the total disorder in the products is lower but not enough lower to make TS greater than H ∆H = (HP-HR) < 0 ∆G = ∆H - T∆S ∆G < 0 ∆S = (SP-SR) < 0

46. Chemical processes tends to proceed spontaneously, If the total bonding forces in the products are weaker than those in the reactants but the entropy increase (increase in disorder) is more than large enough to compensate for the heat absorbed. ∆H = (HP-HR) > 0 ∆G = ∆H - T∆S ∆G < 0 ∆S = (SP-SR) > 0

47. Principle-2 :The gaseous state is more probable than the liquid state, which in turn is more probable than the solid state SOLID  LIQUID  GAS

48. Entropy of Various Substances at 25° (in eu)

49. Principle-3 :A monatomic gas is more probable than a polyatomic molecular gas, and hence tends to have higher entropy MOLECULAR STATE  ATOMIC STATE

50. Entropy of Monatomic and Polyatomic Gas (in eu/g atom)