UNDERSTAND FUGACITY IS A STRICTLY THEORETICAL THERMODYNAMIC CONCEPT THAT MOST PEOPLE HAVE TROUBLE GRASPING- SO DONT WORRY, YOU'RE IT's NOTA PROPERTY THAT YOU CAN DIRECTLY MEASURE, THAT YOU CAN SEE, OR THAT YOU CAN IMMEDIATELY KNOW WITHOUT KNOWING OTHER PROPERTIES ABOUT YOUR ‘SYSTEM AND CHEMICAL SPECIES. WRITTEN By: DANTE SHEPHERD DRAWN By: JOAN COOKE I’M NOT. SURPRISED! BUT IF YOU CAN FOCUS ON THE BASIC CONCEPT AND HOw IT IS APPLIED, IT ‘SHOULD BECOME 'A LOT CLEARER! why IT SEEMS. LIKE SOME KIND OF THEORETICAL NON- SENSE! ‘SURE -- F YOU ONLY FOCUS ON THE TIME YOU SPEND TO CALCULATE IT. tern Unive AdvalTHiS BRINGS US TO CHEMICAL EQUILIBRIUM--HOW EACH CHEMICAL SPECIES WILL BALANCE IN DIFFERENT PHASES PRESENT WITHIN A SYSTEM, LIKE WATER AND OXYGEN PRESENT AS BOTH ‘A GAS AND A VAPOR. THIS CHEMICAL EQUILIBRIUM IS BASED ON GIBBS FREE ENERGY--THE MAXIMUM AMOUNT OF USEFUL WORK THAT CAN BE PULLED FROM A CLOSED SYSTEM. EACH SPECIES PRESENT HAS WHAT ITS OWN PURE FREE GIBBS ENERGY WOULD BE- THE TOTAL ENERGY IT WOULD CONTRIBUTE TO THE MIXTURE ‘AS AN INDIVIDUAL SPECIES. BUT BECAUSE WE DO HAVE DIFFERENT SPECIES PRESENT, THERE IS AN OVERALL GIBBS FREE ENERGY OF THE SYSTEM. WE DEFINE THE CONTRIBUTION OF EACH SPECIES TO THE OVERALL GIBBS FREE ENERGY AS THE CHEMICAL POTENTIAL, [. IT’S THIS CHEMICAL POTENTIAL--WHICH, YES, IS AN ABSTRACT CONCEPT-—-THAT IS THE DRIVING FORCE FOR MASS TRANSFER, FOR SPECIES TO MOVE TO DIFFERENT PHASES: ‘OR DIFFERENT SPACES! THs 1s WHERE FUGACITY COMES IN. 3CHEMICAL POTENTIAL IS A PAIN TO WORK WITH MATHEMATICALLY. BASED ON ITS DEFINTION, FOR CERTAIN CASES LIKE INCREDIBLY SMALL CONCENTRATIONS IN A MIXTURE, CHEMICAL POTENTIAL BECOMES USELESS. THINK OF FUGACITY AS “CORRECTED PRESSURE.” EACH CHEMICAL SPECIES ‘CAN BE DETERMINED FROM THE PRODUCT OF THREE COMPONENTS. WHICH BRINGS US TO FUGACITY. IT'S RELATED TO CHEMICAL POTENTIAL, BUT CAN BE USED WITH GASES, LIGUIDS, OR SOLIDS TO HELP CHARACTERIZE CHEMICAL EGUILIBRIUM! FOR A GAS, WE TAKE THE SPECIES’ CONCENTRATION AND THE SYSTEM PRESURE--THAT COMBINATION ALONE DESCRIBES THE PARTIAL PRESSURE THAT EACH SPECIES NORMALLY TAKES UP WITHIN THE ENTIRE SYSTEM'S PRESSURE. BUT THERE'S A THIRD COMPONENT: A COEFFICIENT TO DESCRIBE HOW IDEAL THE SPECIES IS BEHAVING! HERE IS WHERE THOSE INTERSPECIES INTERACTIONS MATTER SO MUCH! FOR A GAS, THIS COEFFICIENT 1S APTLY NAMED THE FUGACITY COEFFICIENT. A GAS, WE CAN DETERMINE FUGACITY!FOR A LIGUID OR A SOLID, IT'S A LITTLE DIFFERENT. WHILE FUGACITY IS STILL A COMBINATION OF CONCENTRATION, AN IDEALITY COEFFICIENT, AND PRESSURE, YOU NEED TO REMEMBER THAT PRESSURE |S EXERTED A LITTLE DIFFERENT ‘ON LIQUIDS AND SOLIDS THAN ‘ON GASES. FOR LIGUIDS AND SOLIDS, THAT COEFFICIENT SPECIFICALLY DESCRIBING IDEALITY IS THE ACTIVITY COEFICIENT - AGAIN, DESCRIBING THE ACTIVITY OF THE CHEMICAL RELATIVE TO AN IDEAL STATE. SO WE HAVE FOR A UGUID: BUT WHAT SO WHILE CONCENTRATION IS STILL A FACTOR, INSTEAD OF PRESSURE, THE CONTRIBUTING, COMPONENT IS THE “IDEAL FUGACITY,” WHICH CAN BE DETERMINED AS THE FUGACITY OF THE SPECIES WHEN IT IS A PURE SPECIES, = eS ° bb | activity coefficient | 09) 3 4 i & Cnn THAT'S NOT DOES IT ALL WHAT YOURE REALLY ASKING. YOU'RE ASKING, WHY DOES THIS EVEN MATTER, RIGHT?SO IF WE HAVE TWO CHEMICALS PRESENT IN A GAS-LIQUID SYSTEM ~ IF WE CAN DETERMINE THE IDEALITY AND PRESSURE OF THE SYSTEM, ONCE WE KNOW THE CONCENTRATION OF A SPECIES IN ONE PHASE, WE CAN DETERMINE WHAT THE CONCENTRATION IS IN THE OTHER! AND THAT HAS HUGE IMPLICATIONS! THE IMPORTANT THING. TO REMEMBER AFTER WE HAVE CALCULATED ALL OF THESE VALUES IS THAT BASIC RELATIONSHIP DESCRIBING CHEMICAL EQUILIBRIUM- FOR EVERY CHEMICAL PRESENT IN OUR SYSTEM, THE FUGACITY OF THE COMPONENT IN ONE PHASE IS EQUAL TO THE FUGACITY OF THE COMPONENT IN THE OTHER PHASE. WELL, WE CAN APPLY THIS GENERAL RELATIONSHIP TO ANY COMBINATION OF PHASES PRESENT IN A SYSTEM: VAPOR-LIGUID, LIGUID-LIGUID, VAPOR-LIQUID-LIGUID AND SO ON. SO IF WE KNOW WHAT CONCENTRATIONS ARE PRESENT FOR DIFFERENT CONDITIONS, WE WILL KNOW WHAT PHASES WE HAVE PRESENT AND HOW MUCH OF EACH SPECIES IS IN EACH PHASE!WHICH IS USEFUL IN REAL-WORLD APPLICATIONS! FOR EXAMPLE, DISTILATION IS BASED ON THE ENTIRE CONCEPT OF VAPOR-LIQUID EQUILIBRIUM- WE APPLY A RANGE OF TEMPERATURES AND PRESSURES TO BE ABLE TO DRIVE DIFFERENT SPECIES APART--AND KNOWING APPROPRIATE RANGES OF CONCENTRATIONS, BASED ON OUR FUGACITY RELATIONSHIP, ALLOWS US TO OPTIMIZE OUR SYSTEM. WE HAVE SIMILAR RELATIONSHIPS FOR ABSORPTION OF GAS PARTICLES ON A SOLID FILTER SURFACE, OR THE SEPARATION OF CHEMICALS IN IMMISCIBLE LIQUID PHASES--WORKING WITH THE CHEMICAL EQUILIBRIUM EGUATION PRODUCED BY FUGACITY, WE CAN DETERMINE THE OPTIMAL OPERATING CONDITIONS.LET'S LOOK AT SOME EXAMPLES. FIRST, CONSIDER WOULDNT ‘A CASE WHERE WE'VE GOT THEY BOTH GO MIXTURES IN TWO DIFFERENT Pepe fieiGicc aril BEAKERS SEPARATED BY A ‘ THE LARGER VOLUME VALVE, ONE SIDE HAS UST WHEN T TO THE SIDE WITH A LITTLE BIT OF A PURE OPEN THE VALVE, Le5se SUBSTANCE (WE'LL CALL IT WHICH DIRECTION WiLL A.) WHILE THE OTHER SIDE ‘A AND B PARTICLES IS'A LOT OF A $5 A/SR B ‘TRAVEL? MIXTURE. you WOULD THINK THAT—BUT MASS TRANSFER IS DRIVEN By FUGACITY--AND FUGACITY IS PARTLY DEPENDENT ON CONCENTRATION, NOT VOLUME! SO EVEN THOUGH THE SIDE WITH THE MIXTURE SIMILARLY, BY HAS FAR MORE A IN TERMS OF VOLUME THAN CALCULATING THE FUGACITY THE PURE SIDE, WHILE PARTICLES OF B TRAVEL FOR DIFFERENT TEMPERATURES AND FROM THE MIXED SIDE TO THE PURE SIDE, PRESSURES, WE CAN DETERMINE WHAT PARTICLES OF A WILL TRAVEL FROM THE CONCENTRATIONS WE WILL HAVE AND PURE SIDE TO THE MIXTURE! HOW WELL OUR SYSTEMS ARE MIXING, OR SEPARATING!BUT IT GOES FURTHER- THE TERM FOR CHEMICAL EQUILIBRIUM, K, IS DEPENDENT ON THE PRODUCT OF ALL FUGACITIES OF ALL SPECIES PRESENT IN SO, THIS MEANS THAT IF WE CAN CALCULATE THE FUGACITY FOR EACH COMPONENT IN A REACTIVE SYSTEM, THEN WE CAN DETERMINE WHAT THE OUTPUT CONCENTRATION WILL BE FROM A REACTOR! SO THROUGH FUGACITY, WE CAN ACTUALLY DETERMINE HOW EFFECTIVELY A REACTOR 1S WORKING AND HOW MUCH OF OUR DESIRED ‘PRODUCT 1S BEING,‘SO YES, FUGACITY IS COMPLICATED. BUT I'S INCREDIBLY USEFUL WHEN WE REALIZE WHAT IT MEANS AND HOW IT 1S APPLIED! RIGHT! THINK I GET IT. THERE ARE SO MANY EQUATIONS AND DERIVATIONS FOR CALCULATING FUGACITY COEFFICIENTS AND THE OTHER COMPONENTS OF FUGACITY... HANG, IN THERE! FUGACITY IS LATIN FOR “TENDENCY TO ESCAPE”= BUT KEEP AT IT AND IT WONT ESCAPE YOUR BUT WHEN WE PIECE IT ALL TOGETHER, FUGACITY TELLS US WHAT CHEMICALS AND PHASES WE HAVE, AND HOW OUR REACTORS AND SEPARATOR SYSTEMS ARE PROCEEDING! a g 3 AND WHAT A TERRIBLE JOKE TO END ON.