[Corribus]

I believe Atkins and de Paula covers electrochemistry fairly well, although I don't have a copy with me at the moment to check.  The other topics are usually covered in adequate detail in good general chemistry texts, as they are essentially applied thermodynamics issues.  I'm not sure what you mean by "spectroscopic determination calculations". 

[Big-Daddy]

I believe Atkins and de Paula covers electrochemistry fairly well, although I don't have a copy with me at the moment to check.  The other topics are usually covered in adequate detail in good general chemistry texts, as they are essentially applied thermodynamics issues.  I'm not sure what you mean by "spectroscopic determination calculations".

Do you think a text like "Quantitative Chemical Analysis" by Harris would be useful for those topics? Table of contents here: http://www.whfreeman.com/Catalog/product/quantitativechemicalanalysis-eighthedition-harris/tableofcontents It seems to cover a lot of material on all the topics I want. My only worry is that it may not go into sufficient conceptual detail on each one. Do you have any experience of this text?

As for spectrophotometric determination calculations, what I meant might be illustrated with a question:

Solutions containing MoO2S₂^2–, MoOS₃^2– and MoS₄^2– display absorption peaks in the visible wavelength range at 395 and 468 nm. The other ions, as well as H₂S, absorb negligibly in the visible wavelength range. The molar absorptivities (ε) at these two wavelengths are given in the following table:

MoS₄^2–: 120, 11870 (at 395 and 468 nm respectively)
MoOS₃^2–: 9030, 0
MoO2S₂^2–: 3230, 0 (All measured in L/mol/cm)

A solution not at equilibrium contains a mixture of MoS₄^2–, MoOS₃^2– and MoO2S₂^2– and no other Mo-containing species. The total concentration of all species containing Mo
is 6.0×10^–6 M. In a 10.0 cm absorption cell, the absorbance of the solution at 468 nm is 0.365 and at 395 nm is 0.213. Calculate the concentrations of all three Mo-containing anions in this mixture.

(The equilibrium constants for the hydrolysis of MoS₄^2- into finally MoO₄^2- were given previously.) Where do I gain some experience of the theory and calculations behind this kind of question? I've seen it crop up a few times actually ("absorbance", etc.) with regards to equilibrium systems.

[Corribus]

I own a copy of Harris, though I haven't used it much.  From what I can tell, it's a pretty highly regarded intro text to analytical chemistry concepts - which is why I bought it.  Just haven't had a chance to do much with it yet.

With respect to absorption measurements, generally the important point of knowledge here is Beers Law and UV-vis spectroscopy.  Harris may have a good section on this.  I can check tomorrow for you and report back.

[Big-Daddy]

I own a copy of Harris, though I haven't used it much.  From what I can tell, it's a pretty highly regarded intro text to analytical chemistry concepts - which is why I bought it.  Just haven't had a chance to do much with it yet.

With respect to absorption measurements, generally the important point of knowledge here is Beers Law and UV-vis spectroscopy.  Harris may have a good section on this.  I can check tomorrow for you and report back.

Thank you. Please do, whenever you can, don't feel hurried!

Anything which goes up to or above the level of detail which the question I posted seems to call for would be ideal. Looking at the Contents page I think Harris covers equilibria in enough detail (i.e. normal equilibria, "adding" reactions and how to treat multiple equilibria at once, with mass balances, charge balances, and then combining the simultaneous equations); he's got specific sections on solubility and complex formation (combining the two, and/or with acid-base equilibria, should presumably be covered in the "systematic treatment of equilibria" section, i.e. in the combining multiple equilibria tutorial).

Regarding electrochemistry, could I take it that "E° and the Equilibrium Constant" means Harris will cover redox equilibria properly, including the main ionic equilibrium expressions we can write (e.g. to combine redox with other equilibria in a multiple equilibrium system) and also including the relationship between Gibbs' free energy, the equilibrium constant and cell potential, and we'll also go through EMF of the cells itself in some detail?

If you could tell me whether or not I'm being reasonable with these expectations that would be much appreciated! Regarding Beer's Law, I'm sure Harris' section is adequate, but with UV spectroscopy, does he go into enough detail to answer questions like the one I posted?

Thanks a great deal for the help.

[Corribus]

I looked through Harris and it seems like it will cover the areas you are interested in.  Acid-base, spectrophotometry and electrochemistry are all covered in a lot of detail.  It definitely approaches the topics from a chemical analytical viewpoint, but based on the problems you've mentioned, this seems appropriate.

[Big-Daddy]

I looked through Harris and it seems like it will cover the areas you are interested in.  Acid-base, spectrophotometry and electrochemistry are all covered in a lot of detail.  It definitely approaches the topics from a chemical analytical viewpoint, but based on the problems you've mentioned, this seems appropriate.

Thank you.

While I'm not looking for a book that teaches me how to do experiments (a very different skill I wouldn't expect to learn from any book), a systematic - which is what I assume you mean by analytical - approach to these topics (which are: equilibria, including specific parts like acid-base and details like solubility, complex formation, etc., and also redox equilibria, and electrochemistry) which is detailed and thorough is what I need. And of course if you'd recommend Harris, having seen one of these problems of the kind I need to solve, I won't hesitate to buy the book immediately!

Also, are topics regarding electrolysis, like "Faraday's laws of electrolysis, electrolytic conductance, specific, equivalent and molar conductance, and Kohlrausch's law", generally considered as part of electrochemistry or a different field in their own right? And would Harris cover these topics to a high and thorough level as well, or should I look elsewhere for that?

[Corribus]

Generally electrochemistry is primarily concerned with topics related to chemical cells, like Galvanic cells, oxidation/reduction reactions, Nernst equation and so forth.  This is the extent to which it is covered in general chemistry courses, at least here in the US, and in my experience.  Electroanalysis methods like voltammetry, electrolysis are usually not part of the curriculem.  But Harris definitely has a nice chapter dedicated to how these techniques work with numerous practical examples, so if this is a topic you are interested in, the book will cover you well as an broad introduction.  If you want something really in depth, you may consider a book dedicated entirely to the subject, but I'm afraid I cannot recommend one.

[Big-Daddy]

Generally electrochemistry is primarily concerned with topics related to chemical cells, like Galvanic cells, oxidation/reduction reactions, Nernst equation and so forth.  This is the extent to which it is covered in general chemistry courses, at least here in the US, and in my experience.  Electroanalysis methods like voltammetry, electrolysis are usually not part of the curriculem.  But Harris definitely has a nice chapter dedicated to how these techniques work with numerous practical examples, so if this is a topic you are interested in, the book will cover you well as an broad introduction.  If you want something really in depth, you may consider a book dedicated entirely to the subject, but I'm afraid I cannot recommend one.

No problem, it doesn't seem like too much - hopefully I'll be able to pick it up online!

I will take it, then, that you would definitely recommend Harris for me, to cover these details (equilibria and electrochemistry) thoroughly? I only ask again because my budget is limited and there are only so many books I can buy at my stage in education!

McQuarrie and Simon's seems to be very detailed on physical chemistry as well. According to my syllabus it has the odd gap but hopefully nothing I can't fill in online. I might go for it too - considering the "applied" style of my exam's problems, would you recommend it, or something else instead? (based on whatever you've seen so far of the International Chem Olympiad problems) And does the book have nice problems of its own to help test you or is pure theory?

Thanks for all the help so far, it's really appreciated!

[Corribus]

Hmm.  Well, I'm always reluctant to tell people, "You should buy this book."  What constitutes a good textbook is an immensely personal thing, and frankly I think that most peoples' opinions related to what books are good (probably mine included) are heavily influenced by the experience they had in the class they used it.  This is particularly the case when people think a book is bad.  I wager most of the people who don't like McQuarrie and Simon - and there are lots of them - aren't judging the book so much as the professor who commanded they buy it.  Of course, if you are taking a class in a subject, you don't really have a choice of what book to buy - you buy what the class uses - but if you are buying a book for your own use, then you have options, and I think it's always best in that case to get a copy of the book you're thinking of buying before you buy it.  If you can't find a friend who has it, most University libraries can request a copy through interlibrary loan.  Check it out for a month, read through some of it, see if it has what you want.  Going by reviews and personal recommendations is helpful, but it's hard to know what reviews are biased by things not related to the text itself and even if you trust the person making the recommendation, they really don't know what exactly you're looking for.

Anyway, I've always liked McQaurrie and Simon, but there are plenty of people who hate it.  But there are plenty of people who hate every physical chemistry textbook.  It's math heavy, for one thing, and doesn't have the best figures in the world.  What I like about it is that it starts with quantum first and builds thermodynamics and everything else off of that, which is in my opinion how physical chemistry should be taught.  Atkins is probably a more approachable text, but the idea of teaching thermo first is somewhat antequated in my view.  No matter what book you choose, physical chemistry isn't the easiest subject to teach yourself.  It's all about concepts, difficult concepts, and for this kind of material I really think you need a capable instructor.  Even then you probably won't truly understand it - I think it takes trying to teach it yourself before it really starts to make any kind of sense.  That's the way it worked for me, anyway.

So all that said, though I think M&S is the superior text and it's what I would use were I teaching the subject, if you are buying a textbook to use on your own, without external instruction, Atkins may be the better choice.

As for Harris - my recommendation is only superficial.  I don't have any experience using it in a class or teaching from it.  Mostly it's just from page-flipping.  It seems to be an excellent book geared toward chemical analysis and covers the topics you have mentioned in good detail.  I have not done any problems in the book so cannot comment on them.  But I can say that it goes over analytical techniques in good detail in addition to just giving conceptual information.  There are also several chapters on statistical analysis as well as chapters on common laboratory techniques like mass spec, HPLC, and so forth - stuff that is rarely found in general chemistry texts anymore and even less frequently taught in general chemistry coursework. 

[Will you pardon a three second rant? The fact that chemistry curricula at most US universities don't include an analytical course like this (mine didn't) is a shame and the lack of statistics requirement, even a small section in general chemistry class, is borderline criminal.]

Anyway, if all that sounds like I'm backing off because I don't want to be accused later on of leading you to buy something you ultimately think was a waste of money, well... you'd be right.   I guess what I'm saying is that while I know M&S is a good p-chem textbook, even if it would be a hard read for a beginner, and Harris seems like a good analytical textbook, your best bet is to try to get a copy of any book you are considering buy and take a look at it yourself.  In the end only you will be able to decide whether it covers the topics you need in a way that agrees with your learning style.  It's better to find that out before you lay down upwards of $50-100.  The good news is, of course, that you can always turn around and re-sell it on Amazon if you have to.

[Big-Daddy]

Hmm.  Well, I'm always reluctant to tell people, "You should buy this book."  What constitutes a good textbook is an immensely personal thing, and frankly I think that most peoples' opinions related to what books are good (probably mine included) are heavily influenced by the experience they had in the class they used it.  This is particularly the case when people think a book is bad.  I wager most of the people who don't like McQuarrie and Simon - and there are lots of them - aren't judging the book so much as the professor who commanded they buy it.  Of course, if you are taking a class in a subject, you don't really have a choice of what book to buy - you buy what the class uses - but if you are buying a book for your own use, then you have options, and I think it's always best in that case to get a copy of the book you're thinking of buying before you buy it.  If you can't find a friend who has it, most University libraries can request a copy through interlibrary loan.  Check it out for a month, read through some of it, see if it has what you want.  Going by reviews and personal recommendations is helpful, but it's hard to know what reviews are biased by things not related to the text itself and even if you trust the person making the recommendation, they really don't know what exactly you're looking for.

Anyway, I've always liked McQaurrie and Simon, but there are plenty of people who hate it.  But there are plenty of people who hate every physical chemistry textbook.  It's math heavy, for one thing, and doesn't have the best figures in the world.  What I like about it is that it starts with quantum first and builds thermodynamics and everything else off of that, which is in my opinion how physical chemistry should be taught.  Atkins is probably a more approachable text, but the idea of teaching thermo first is somewhat antequated in my view.  No matter what book you choose, physical chemistry isn't the easiest subject to teach yourself.  It's all about concepts, difficult concepts, and for this kind of material I really think you need a capable instructor.  Even then you probably won't truly understand it - I think it takes trying to teach it yourself before it really starts to make any kind of sense.  That's the way it worked for me, anyway.

So all that said, though I think M&S is the superior text and it's what I would use were I teaching the subject, if you are buying a textbook to use on your own, without external instruction, Atkins may be the better choice.

As for Harris - my recommendation is only superficial.  I don't have any experience using it in a class or teaching from it.  Mostly it's just from page-flipping.  It seems to be an excellent book geared toward chemical analysis and covers the topics you have mentioned in good detail.  I have not done any problems in the book so cannot comment on them.  But I can say that it goes over analytical techniques in good detail in addition to just giving conceptual information.  There are also several chapters on statistical analysis as well as chapters on common laboratory techniques like mass spec, HPLC, and so forth - stuff that is rarely found in general chemistry texts anymore and even less frequently taught in general chemistry coursework. 

[Will you pardon a three second rant? The fact that chemistry curricula at most US universities don't include an analytical course like this (mine didn't) is a shame and the lack of statistics requirement, even a small section in general chemistry class, is borderline criminal.]

Anyway, if all that sounds like I'm backing off because I don't want to be accused later on of leading you to buy something you ultimately think was a waste of money, well... you'd be right.   I guess what I'm saying is that while I know M&S is a good p-chem textbook, even if it would be a hard read for a beginner, and Harris seems like a good analytical textbook, your best bet is to try to get a copy of any book you are considering buy and take a look at it yourself.  In the end only you will be able to decide whether it covers the topics you need in a way that agrees with your learning style.  It's better to find that out before you lay down upwards of $50-100.  The good news is, of course, that you can always turn around and re-sell it on Amazon if you have to.

Thank you, this is immensely helpful. I will try and get my library to order a copy. Your recommendation on Harris seems strong and others have recommended it too so I will endeavour to acquire it; as for McQuarrie and Simons, on the face of it I think I would prefer this book to Atkins simply because it covers more of the topics I want, but on the other hand - and this is just hypothesizing, I will try and get the book - the style of problems is probably better for me in Atkins, because our problems require a much more "applied" understanding (e.g. I would probably like a couple of problems just to cover the fact that, like enthalpy, entropy and Gibbs' free energy are additive, and can be found from equations of formation or combustion too, and in general operate the same way as enthalpy for a set group of reactions when we are just manipulating one of these three thermodynamic factors without considering the others - this just being an example of a fact that was not immediately obvious to me and on which I would like at least a little bit of practice to be in the book!). Let me give you an example (related to vapor pressures and the Clausius-Clapeyron example, only designed to give a flavour of what sort of applications the Olympiad asks for from our knowledge):

A British artist Roger Hiorns entirely filled a flat with a supersaturated copper sulfate solution. After removal of the solution, blue crystals remained on the walls, floor, and ceiling.

1. Write down the formula of these crystals. Covered in any inorganic chemistry book, probably - CuSO4.5H2O.

2. Humidity inside this flat has a constant low level. Using the Clausius-Clapeyron equation, calculate the temperature at which the humidity will be 35% (of the saturated vapor pressure of water at the same temperature). This is what I mean by "applied" question.

Copper sulfate is often used in laboratories as a drying agent, for example, to obtain absolute ethanol. By rectification of aqueous ethanol one can increase its concentration to not more than 95.5 wt.%. For further dehydration of ethanol, anhydrous copper sulfate is added. After a while the liquid is decanted and treated with a new portion of anhydrous copper sulfate. These operations are repeated 2-3 times until copper sulfate will stop turning blue. Then ethanol is filtered and distilled.

3. What is the minimum residual water content (in mass percent) that can be achieved by
using this method at room temperature?

Two chemists argued at what temperature – high or low – should the process of drying be
performed in order to achieve lower residual water content.

4. Calculate the minimum residual water contents if ethanol was dried at 0 °C and 40 °C.

Given pieces of information were the saturated vapor pressures and enthalpies of formation of 6 different forms of copper sulphate crystal, and the fact that vapor pressure of water over its dilute solution in ethanol is given by vapor pressure=saturated vapour pressure * mole fraction of water * activity coefficient of water (assumed at 2.45).

So hopefully that is a good example of how we need to be able to apply the knowledge directly. I suspect Atkins' Physical Chemistry would be better at gearing towards these sorts of questions than the more deeply theoretical, less applied McQuarrie and Simons textbook (which may not have many questions which relate back to the applications, like this example does)? Or which textbook might I look up or request from my library along the line of this style of problem? The textbook needn't actually ask problems like this (though that would be ideal), merely incline towards keeping a student's understanding at this fundamental, applied level so they could then be best prepared to answer questions like this from the theory in the book.

[Big-Daddy]

Having just looked into Atkins' Physical Chemistry in some detail, I think it's great book which should definitely be enough for a first-year university student or someone preparing for the IChO. Topics on the IChO "Advanced" list for physical chemistry are largely covered in the book itself and the level seems neither too high nor too low (obviously the question style is somewhat different but that's expected).

[mina]

if you simply attempt to study basics in physical chemistry both Atkins and Levine books are extremely useful depending on the major you are in you can chose one of them easily if you are a pure chemistry student or some thing and you will face this principles in future frequently you have to be really careful Atkins and Levine's physical chemistry books are perfect but Levine goes through the details more than Atkins in thermodynamic concepts. In kinetic Atkins book contain several titles that are some how advanced sometimes and not really necessary for a BA chemistry student. but Levine's kinetic chapter is much simpler..
If you are new to physical chemistry it is not really necessary to be worry about statistical thermodynamics but I believe in this field McQarrie's statistical thermodynamic is a good book. before starting with quantum mechanics make sure you know enough mathematical background and do not study by your self I advise you. in spectrophotometry Harris book maybe is not the most complete one but fore sure is one of the most simplest books in spectrophotometry ever. 
 you will understand which chapter suit you more in which book by studying in several books... do not limit yourself in one book... physical chemistry is the most challenging field among chemistry students some hate it most and some love it...

     

[Big-Daddy]

you have to be really careful Atkins and Levine's physical chemistry books are perfect but Levine goes through the details more than Atkins in thermodynamic concepts. In kinetic Atkins book contain several titles that are some how advanced sometimes and not really necessary for a BA chemistry student. but Levine's kinetic chapter is much simpler..
   

Really? I have Atkins, not Levine, but I think that Atkins goes into a lot of detail on thermodynamics and ΔG. Not as much as calculus-based texts such as McQuarrie and Simons', but still quite a lot. I would recommend the Thermodynamics Oxford Chemistry Primer more than anything else for thermo though.

I'm thinking anyone wanting to get to a good level on physical and physical/analytical chemistry should study:

Atkins "Physical Chemistry"
Harris "Quantitative Chemical Analysis"
Oxford Chemistry Primers: "Electrode Potentials" (Compton), "Thermodynamics"

OCP on "Electrode Dynamics" may be good, I can't say as I haven't read it yet. I think it will cover topics like electrolysis.

[sario]

I think that it depends from the field of physical chemistry. For Quantum mechanics I like Levine - Quantum Chemistry. For thermodynamics I suggest Chang - Physical Chemistry but if you want a great book, you will read Enrico Fermi - Thermodynamics. That's all!

[Benzene Martini]

For me, nothing helped. I got through P Chem 1 with a "B-" and withdrew from P Chem 2.

I retook P Chem 2 and was happy with my "C".

I may be using P Chem knowledge everyday, but I will never know because I didn't understand what was going on! Deriving equations taught me nothing.

The labs were not even fun. They were taught by grad students that didn't understand them. This was because the professor did not understand the experiments. He had all of the theoretical knowledge, but seemed to be confused in lab.

Oh well, I graduated.