ENTROPY MEANING OF THE TERM?

CLUE WHAT 8 LETTER WORD INDICATES THE CONDITION OF THE CLASS IN THE ABSENCE OF THE TEACHER

ENTROPY
DISORDER DENOTED BY S IS A MEASURE OF DISORDER OF A SYSTEM IT CAN BE ZERO AT ZERO KELVIN AND THIS ASSUMES A PERFECTLY ORDERED CRYSTAL  AS TEMPERATURE OF THE MATERIAL INCREASES,THE PARTICLES GAIN KINETIC ENERGY AND THEIR MOTION INCREASES  HIGH TEMPERATURE INCREASE THE DISORDER OF THE SYSTEM
   

CHANGE IN ENTROPY
 HOW DOES ENTROPY CHANGE WITH CHANGE OF STATE FROM

 SOLID

LIQUID

GAS

CHANGE IN ENTROPY

CHANGE IN ENTROPY WITH TEMP.

ENTROPY CHANGE WHEN DISSOLVING

 

IONS IN A SOLID ARE ORDERED DISSOLVING THE IONIC SOLID IN WATER CAUSES THE ENTROPY TO INCREASE

CHANGE IN ENTROPY
ENTROPY INCREASES WHEN THE NUMBER OF PARTICLES INCREASE
CHANGE REACTION RELEASING A GAS EG Zn AND ACID CHANGE IN ENTROPY POSITIVE INCREASING ENTROPY REASON GAS MOLECULES ARE MORE DISORDERED THAN THAT IN SOLUTION LESS MOLECULES OF PRODUCTS THAN REACTANTS REDUCING

GAS REACTION WHERE NO. OF MOLECULES DECREASE

FORMATION OF NEGATIVEAMMONIA DREASING ENTROPY

CALCULATING CHANGE IN ENTROPY S

 ENTROPY VALUES DEPEND ON TEMPERATURE AND PHYSICAL STATE  ENTROPY INCREASE AS NO. OF BONDS IN THE SUBSTANCE INCREASE.EG ETHANOL HAS GREATER ENTROPY THAN METHANOL  STANDARD ENTROPY IS THE ENTROPY OF A SUBSTANCE AT STANDARD TEMPERATURE AND PRESSURE AND IS EXPRESSED PER MOLE OF THE SUBSTANCE

CALCULATING CHANGE IN ENTROPY S

 THE STANDARD ENTROPY CHANGE FOR PHYSICAL OR CHEMICAL CHANGE IS THE DIFFERENCE IN ENTROPIES OF THE PRODUCTS AND REACTANTS MEASURED UNDER STANDARD CONDITION

ENTROPY CHANGE OF SYSTEM =TOTAL ENTROPY OF PRODUCTS-TOTAL ENTROPY OF REACTANTS  S= S OF PRODUCTS- S OF REACTANTS

RELATION BETWEEN ENTHALPY AND ENTROPY

 EXOTHERMIC REACTIONS GIVE OUT HEAT ,INCREASES THE ENTROPY OR DISORDER OF THE SURROUNDING PARTICLES AND ARE SPONTANEOUS  SOME ENDOTHERMIC REACTIONS WHICH HAVE POSITIVE VALUE FOR H ALSO ARE SPONTANEOUS AT ROOM TEMPERATURE.  ENTHALPY CHANGES ALONE DO NOT DITERMINE WHETHER A REACTION IS SPONTANEOUS OR NOT

 TOTAL ENTROPY CHANGE DITERMINES WHETHER A REACTION IS SPONTANEOUS OR NOT.

S TOTAL = SSYSTEM + SSURROUNDING  S SURROUNDING = - H  T  FOR ANY SPONTANEOUS CHANGE TOTAL ENTROPY SHOULD BE POSITIVE


FEASIBILITY OF A REACTION
IB Chemistry_Relating enthalpy and entropy to spontaneity

 FEASIBILITY OF A REACTION IS RELATED TO BOTH ENTROPY AND ENTHALPY CHANGES  IF S TOTAL> O ,REACTION WILL BE FEASIBLE

 THE MAIN FACTORS WHICH DITERMINE FEASIBILITY OF A REACTION ARE  1.ENTROPY CHANGE OF THE SYSTEM  2.TEMPERATURE MEASURED IN KELVIN  3.ENTHALPY CHANGE WITH THE SURROUNDING.

THERMODYNAMIC STABILITY AND KINETIC STABILITY

IF S total IS POSITIVE REACTION IS FEASIBLE AND THE REACTANTS ARE SAID TO BE THERMODYNAMICALLY UNSTABLE RELATIVE TO THE PRODUCTS IF S total IS NEGATIVE REACTION IS NOT FEASIBLE AND THE REACTANTS ARE SAID TO BE THERMODYNAMICALLY STABLE RELATIVE TO THE PRODUCTS

THERMODYNAMIC STABILITY AND KINETIC STABILITY

 A SMALL ACTIVATION ENERGY MEANS A REACTION IS SPONTANEOUS AND REACTANTS ARE KINETICALLY UNSTABLE RELATIVE TO THE PRODUCTS  A HIGH ACTIVATION ENERGY MEANS REACTANTS ARE KINETICALLY STABLE RELATIVE TO THE PRODUCTS

 USE THE FOLLOWING DATA TO EXPLAIN WHY THE CONVERSION OF DIAMOND TO GRAPHITE IS FEASIBLE AT ALL TEMP. BUT DOES NOT OCCUR AT ROOM TEMP.

STANDARD ENTROPY  DIAMOND 2.4J/mol/k  GRAPHITE 5.7  H diamond to graphite=-2kj/mol



   

H diamond to graphite is negative showing the reaction is exothermic and diamond is thermodynamically unstable S system=5.7-2.4=3.3 S surrounding= + value S total is positive so reaction is feasible at room temp. Reaction does not take place at room temp. because it has high activation energy, so the reactant is kinetically stable

THERMODYNAMIC STABILITY AND KINETIC STABILITY

 EG. COMBUSTION OF METHANE

S TOTAL IS POSITIVE AND SO THE REACTION IS THERMODYNAMICALLY FEASIBLE OR THE REACTANTS ARE SAID TO BE THERMODYNAMICALLY UNSTABLE RELATIVE TO THE PRODUCTS  THE REACTION DOES NOT TAKE PLACE AT ROOM TEMPERATURE SO THE ACTIVATION ENERGY MUST BE HIGH SO THE REACTANTS WILL BE KINETICALLY INERT RELATIVE TO THE PRODUCTS


ENTHALPY CHANGES AND DISSOLVING

 WHEN IONIC SOLIDS DISSOLVE IN POLAR SOLVENTS TWO ENTHALPY CHANGES OCCUR  LATTICE ENERGY-THE SOLID MUST SEPARATE INTO IONS.THIS IS AN ENDOTHERMIC CHANGE  HYDRATION ENTHALPY-THE SEPERATED IONS INTERACT WITH THE POLAR SOLVENT.THIS IS AN EXOTHERMIC CHANGE

9-10-2011
 Learning objective 1.understand enthalpy of hydration and lattice enthalpy and the factors affecting them  2.calculate enthalpy of solution and draw hess s cycle  3.predict solubility from enthalpy of solution data

Learning outcome
 Will be able to calculate enthalpy of solution and draw hess s cycle  Will be able to predict solubility from enthalpy of solution data 

ENTHALPY CHANGES AND DISSOLVING

 ENTHALPY OF SOLUTION OF AN IONIC SOLID,

H solution= - H lattice energy+ Hhydration H solution CAN BE POSITIVE OR NEGATIVE



ENTHALPY CHANGES AND DISSOLVING

 A POSITIVE H solution CORREPONDS TO AN ENDOTHERMIC CHANGE AND DISSOLVING IS NOT FAVOURED BUT THE SUBSTANCE WILL DISSOLVE IF TOTAL ENTROPY IS POSITIVE.  A NEGATIVE H solution CORRESPONDS TO AN EXOTHERMIC CHANGE,SO DISSOLVING IS FAVOURED

ENTHALPY CHANGES AND DISSOLVING

 USE THE FOLLOWING DATA TO PREDICT WHETHER THE SUBSTANCES WILL DISSOLV E OR NOT,AT TEMP298K
SUBSTANCE LiCl NaCl AgCl Magnesium sulfate H solution kj/mol -37 +4 +66 -91 Ssystem j/mol +11
43

+33 -213

ENTHALPY CHANGES AND DISSOLVING

 lithium chloride will dissolve because of negative value of enthalpy of solution and positive value of entropy of system  FOR SUBSTANCE WITH POSITIVE VALUE OF ENTHALPY OF SOLUTION ,IT WILL DISSOLVE IF TOTAL ENTROPY IS POSITIVE  FOR Nacl IT IS GREATER THAN ZERO SO IT WILL DISSOLVE  FOR AgCl the value is negative so it will not dissolve

CALCULATION OF ENTHALPY OF HYDRATION OR SOLUTION FROM HESS S CYCLE

 STANDARD ENTHALPY OF HYDRATION OF AN ION IS THE ENTHALPY CHANGE WHEN ONE MOLE OF THE GASEOUS IONS IS HYDRATED UNDER STANDARD CONDITIONS WHERE FURTHER DILUTION WOULD CAUSE NO FURTHER ENTHALPY CHANGE

FACTORS EFFECTING LATTICE ENTHALPY

 CHARGES ON ION-GREATER THE PRODUCT OF THE CHARGES ON IONS GREATER THE LATTICE ENERGY  RADII OF THE IONS-SMALLER THE SUM OF THE RADII OF THE IONS GREATER THE LATTICE ENERGY  QUES.WHICH OF THE FOLLOWING WILL HAVE MORE LATTICE ENERGY KCl OR NaCl

ENTHALPY CHANGES AND DISSOLVING

 PRODUCT OF CHARGE IS SAME FOR BOTH  SUMOF RADII IS GREATER FOR KCl THAN FOR NaCl ,SO IT HAS LOW LATTICE ENRGY COMPARED TO NaCl

CHANGE IN LATTICE ENERGY

 AS THE SIZE OF THE CATION INCREASE DOWN THE GROUP LATTICE ENERGY DECREASES  AS THE SIZE OF THE ANION INCREASES DOWN THE GROUP LATTICE ENERGY DECREASES  WHEN THE CHARGE OF THE CATION OR ANION INCREASES LATTICE ENERGY INCREASES

FACTORS EFFECTING HYDRATION ENTHALPY

 MAGNITUDE OF HYDRATION ENTHALPY DEPENDS ON THE STRENGTH OF THE FORCE BETWEEN THE IONS AND THE WATER MOLECULES SURROUNDING THEM  GREATER THE CHARGE-GREATER THE FORCE  SMALLER THE RADIUS GREATER THE FORCE

 THE IONIC RADII OF AN ION OF +2 CHARGE IS O.O31 AND THAT OF AN ION OF CHARGE +3 CHARGE IS O.O95  WHICH HAS HIGHER EXOTHERMIC ENTHALPY OF HYDRATION

 FOR THE ION OF CHARGE +2 CHARGE/RADIUS IS 65  FOR THE ION OF CHARGE +3 CHARGE/RADIUS IS 32  THE ION OF CHARGE +2 HAS LARGER CHARGE DENSITY SO ITS HYDRATION ENERGY WILL BE MORE EXOTHERMIC

EXTEND OF SOLUBILITY
 AN IONIC SOLID DISSOLVES IF TOTAL ENTROPY IS A POSITIVE VALUE  ENTROPY OF SYSTEM OF IN IONIC SOLID IS THE SUM OF THE ENTROPY OF THE SOLUTE AND SOLVENT  IN MOST OF THE SOLUTIONS ENTROPY INCREASES WHEN MIXED WITH SOLUTE PARTICLES

EXTEND OF SOLUBILITY
 CERTAIN AMOUT OF ORDERING OF SOLVENT MOLECULES HAPPEN WHEN THEY SURROUND THE IONS  THIS ORDERING DEPENDS ON THE CHARGE DENSITY OF THE ION  IN GROUP ONE, LITHIUM ION CAUSES MORE ORDERING, AND DECREASES THE ENTROPY OF THE SOLVENT MORE THAN THE REST OF THE IONS,WHY?

EXTEND OF SOLUBILITY
 GROUP II IONS HAVE MORE CHARGE DENSITY THAN GROUP I SO ENTROPY OF SOLVENT STILL DECREASES  HOW DOES THE ENTROPY OF SYSTEM VARY DOWN GROUP II ?

EXTEND OF SOLUBILITY
 AS THE CHARGE DENSITY DECREASES DOWN THE GROUP THE ORDERING OF THE SOLVENT DECREASES AND ENTROPY OF SYSTEM INCREASE DOWN THE GROUP.  BARIUM IONS ORDER WATER LESS THAN MAGNESIUM IONS

EXTEND OF SOLUBILITY
 ENTROPY OF SYSTEM OF GROUP I ,AMMONIUM AND SILVER COMPOUNDS ARE POSITIVE SINCE THEY CAUSE A SMALL ORDERING OF THE SOLVENT  GROUP II COMPOUNDS CAUSE MORE ORDERING OF THE SOLVENT SO THEIR ENTROPY OF SYSTEM IS NEGATIVE

EXTEND OF SOLUBILITY
H solution endothermic endothermic S system If more positive than S surr If negative or less positive than S surr Positive or less negative than S surr More negative than S surr solubility soluble insoluble

exothermic exothermic

soluble insoluble

SOLUBILITY TREND IN GROUP

 ENTHALPY OF SOLUTION DEPENDS ON LATTICE ENERGY AND HYDRATION ENTHALPY  IN A GROUP LATTICE ENERGY AND HYDRATION ENTHALPY BECOMES LESS EXOTHERMIC AS WE COME DOWN THE GROUP  IF LATTICE ENERGY DECREASES MORE THAN HYDRATION ENTHALPY THE ENTHALPY OF SOLUTION BECOMES MORE EXO DOWN THE GROUP

  Mg(OH)2  Ba(OH)2 

L.E -2842 -2228 614

H.E -1920 -1360 560

CHANGE

TREND FOR GRP.2 HYDROXIDES

 SOLUBILITY INCREASES DOWN THE GROUP  LATTICE ENERGY DECREASES MORE THAN HYDRATION ENTHALPY  ENTHALPY OF SOLUTION BECOMES MORE EXOTHERMIC

TREND FOR GRP.2 SULPHATES

 DOWN THE GROUP HYDRATION ENTHALPY DECREASES MORE THAN LATTICE ENERGY  ENTHALPY OF SOLUTION BECOMES LESS EXOTERMIC DOWN THE GROUP  SOLUBILITY DECREASES

TREND FOR SILVER HALIDES

 ENTHALPY OF SOLUTION BECOMES MORE ENDOTHERMIC DOWN THE GROUP

S surrounding BECOMES MORE NEGATIVE DOWN THE GROUP  SOLUBILITY DECREASES DOWN THE GROUP