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Questions tagged [thermodynamics]

Applicable to questions about heat, energy, work, and their interconversion in chemistry. See the tag wiki for a detailed list of topics. Questions tagged may also be tagged with [enthalpy], [energy], [free-energy] where appropriate.

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Is there a general consensus on the causes of the alpha-effect?

There have been various explanations posited for the α-effect. The α-effect refers to a phenomenon wherein nucleophiles with lone pairs on atoms adjacent (i.e., in the α- position) to the atom bearing ...
90
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8answers
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Why is absolute zero unattainable?

We were dealing with the Third Law of Thermodynamics in class, and my teacher mentioned something that we found quite fascinating: It is physically impossible to attain a temperature of zero ...
41
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3answers
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Unit of the equilibrium constant: contradiction of Bridgman's theorem?

The following equation is standard in thermodynamics: $$ \Delta G^\circ=-RT\log(K) $$ where $K$ is the equilibrium constant. In dimensional analysis, Bridgman's theorem tells us that the argument ...
39
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3answers
11k views

Why do impurities lower the melting point of an isolated substance?

It is known that impurities in a desired isolated product lower the melting point of the mixture, even if the impurities' melting point is much higher than the desired product. Why is that so?
35
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4answers
3k views

Does any known substance ignite on cooling?

As the title says, I'm interested in knowing if there is any substance — or combination of substances — that ignites (or even increases its chance of spontaneous ignition) when cooled. I've never ...
33
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5answers
102k views

Difference between thermodynamic and kinetic stability

What is the difference between thermodynamic and kinetic stability? I'd like a basic explanation, but not too simple. For example, methane does not burn until lit -- why?
28
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4answers
86k views

Difference between exothermic and exergonic

In High School I learned that an exothermic reactions releases energy, while an endothermic reaction needs energy to occur. Now I learned that there is a separate, somewhat similar classification ...
27
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3answers
22k views

Why do salts such as NaCl dissolve?

If we look at solubility of salts in water, we are told that they disassociate, because the positive $\ce{Na}$ ion is attracted to the partially negative oxygen in water and the negative $\ce{Cl}$ is ...
26
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4answers
7k views

Why do chemistry and physics have different sign convention in thermodynamics?

In physics class, we write the first law of thermodynamics as $\mathrm dU =\mathrm dQ - \mathrm dW$ and in the physical chemistry class, we write the same law as $\mathrm dU =\mathrm dQ + \mathrm dW$. ...
26
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4answers
13k views

What is the difference between ∆G and ∆G°?

In Brady's Molecular Nature of Matter, I read that $\Delta_\mathrm{r} G^{\circ}$ is $\Delta_\mathrm{r} G$ at $25~^\circ\mathrm{C}$. But later, it gives a value for $\Delta_\mathrm{r} G^\circ$ at ...
25
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4answers
18k views

Hypothetical: What happens to water as pressure increases to infinity? [duplicate]

I've asked a similar question here but the answer given shows the behaviour of water under general conditions. I'd like to know what the behaviour of water is like as pressures increase towards ...
25
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1answer
237 views

When measuring avidity should you use the ligand concentration or the nanoparticle concentration?

Looking at avidity between a ligand-receptor, you're looking at an enhancement of the $K_d$ compared to a lone ligand. Is it more appropriate to compare the $K_d$ using the concentration of the "...
24
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2answers
12k views

What is known about liquid carbon?

The wiki tells me that if you heat carbon at atmospheric pressure it eventually turns directly into a gas without being liquid first. At what pressure can you make liquid carbon? Has anyone actually ...
23
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2answers
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Michael reaction or nucleophilic attack at the alpha carbon of an alpha-beta-unsaturated ketone?

What conditions promote a nucleophile to undergo the Michael reaction over the nucleophilic attack at the alpha carbon of the carbonyl group in an alpha-beta-unsaturated ketone? I'm looking for an ...
22
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4answers
10k views

Why does water evaporate spontaneously at room temperature despite ΔG > 0?

Standard Gibbs free energy of formation of liquid water at $\pu{298 K}$ is $\pu{−237.17 kJ mol-1}$ and that of water vapour is $\pu{−228.57 kJ mol-1}$ therefore, $$\ce{H2O (l) -> H2O (g)}\qquad\...
22
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4answers
936 views

What is the origin of the maximum in rotational heat capacity?

The graph of rotational heat capacity above shows a small maximum before approaching the equipartition value. What is the origin/physical explanation of this maximum?
21
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1answer
2k views

If aliens lived in a hydrogen (or any flammable gas) based atmosphere, would they perceive oxygen to be flammable?

Energy, fuel, and oxygen are needed for a fire to burn. In a hydrogen chamber, if there was a pipe spewing small amounts of oxygen, could you light the oxygen on fire as it began to mix with the ...
21
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1answer
3k views

What is behind of the attraction between a burned matchstick with a magnet?

I do not know how to understand the reasons of why a burned matchstick is attracted by a magnet (most probably) of Neodymium. Here are some screenshots of a video in which this natural phenomenon is ...
20
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3answers
5k views

What are the chemical reactions behind fire?

I've always wondered what the chemistry behind fire is. What are the basic chemical reactions behind a simple wood fire, and how do they manifest into this phenomenon?
20
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1answer
5k views

Why is NaCl3 possible?

There. And there. Almost a year ago, a group of scientists claimed to have reached compounds of $\ce{Na}$ and $\ce{Cl}$ with weird stochiometries ($\ce{NaCl3, Na3Cl, NaCl7, Na3Cl2}$ and $\ce{Na2Cl}$). ...
19
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5answers
47k views

Why does hydrogen fluoride have a boiling point so much lower than that of water?

$\ce{F}$ has more unshared electron pairs and is very electronegative, so $\ce{H}$ of another $\ce{HF}$ molecule can $\ce{H}$-bond with it. $\ce{HF}$ has normal boiling point of $\pu{19.5^oC}$ while $...
19
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1answer
4k views

Why can't helium be solidified at 'ordinary' pressures?

According to the UC Davis ChemWiki Chemistry of Helium, helium has a comparatively unusual property, specifically: Helium is the only element that cannot be solidified by lowering the temperature ...
19
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4answers
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Is not possible to find absolute value of internal energy?

Today in thermodynamics lecture my teacher told that it is not possible to find absolute value of internal energy so we have to calculate change in internal energy. So my question is why is it not ...
19
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2answers
783 views

What causes the “Gd break” in the trend of lanthanide-EDTA formation constants?

Smith and Martell obtained a series of data for the binding of trivalent lanthanide ions, $\ce{Ln^3+}$, with various carboxylic acid ligands (amongst them the well-known EDTA).1 A graph of the ...
19
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1answer
777 views

Deliquescence/efflorescence: How can I convert between salt concentration and RH?

I am looking at two phase diagrams, one has axes of $T$ and $\%\ce{MgClO4}$ in a $\ce{H2O-MgClO4}$ mix, and the other has axes of $T$ and relative humidity. The authors of the second phase diagram say ...
18
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2answers
2k views

What is a rigorous definition of gas volume, and how is the Van der Waals equation derived?

I am confused about the justification for the corrections to the ideal gas law in the Van der Waals equation: $$p=\frac{nRT}{V-nb}-a\left(\frac{n}{V}\right)^2$$ I understand that the equation ...
18
votes
1answer
2k views

Why is chemical accuracy defined as 1 kcal/mol?

"Chemical accuracy" in computational chemistry, is commonly understood to be $1~\mathrm{kcal\over mol}$, or about $4~\mathrm{kJ\over mol}$. Spectroscopic accuracy is $1~\mathrm{kJ\over mol}$, and that ...
18
votes
1answer
554 views

What is the relation between surface tension and initial molecular harmonic?

Initial harmonic is measured as Hartree/Bohr^2 ( like IHarmonic=n in Gaussian Software ). As I am from physics background I am used to look at features from their dimension point of view: Actually ...
17
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7answers
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If the human body consists of 60% water why can't we put out fire with our body? [closed]

I have often heard of people being burned at the stake, but if the body is 60% water shouldn't the fire just be put out?
17
votes
1answer
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Why is acetone so cold?

I have a summer job as a custodian and one cleaner I use is called Goof Off, which is pretty much just acetone. Another is a disinfectant which is mostly water. How come whenever I put the acetone on ...
17
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5answers
2k views

Is enthalpy additive in mixing?

When mixing two fluids of different composition at constant pressure when no heat can escape, is the enthalpy additive? If not, how to compute the enthalpy of the mixture resulting from mixing two ...
17
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2answers
2k views

Formula of entropy change

In my 12th standard book, the formula for entropy change is given as $\Delta S = \frac{q_\text{reversible}}{T}$. What is the importance of absorbing heat reversibly and not irreversibly? What does ...
17
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1answer
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Can entropy increase during bond formation?

Recently the question was asked, "Is bond formation “strictly” exothermic?" As a corollary to that question, what is the relationship between entropy and bond formation? Does the entropy of the bond ...
16
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3answers
2k views

How to evaluate the heat of formation with computational chemistry?

I'm sorry if this is a stupid question, but since I'm a beginner with computational chemistry, please, be patient. Let's consider the reaction of formation of water: $$\ce{1/2 O2(g) + H2(g) -> ...
16
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2answers
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Why does the reaction quotient use the products (multiplications) of reactants and products, rather than their respective sums?

As you may know, the reaction quotient $Q_c$ is defined by the equation $$ Q_c = \frac{[C]^\gamma [D]^\delta}{[A]^\alpha [B]^\beta} $$ for the chemical reaction $$ \alpha A + \beta B \rightarrow \...
16
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3answers
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On adding sugar to water, does the entropy increase or decrease?

This question is a little confusing. According to my teacher, the entropy should decrease, but I think that sugar is crystalline first and later it dissolves, so the randomness increases and so the ...
16
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2answers
17k views

Why is dU an exact differential and dq an inexact differential?

dU, dG, dH etc are all exact differentials and the variables themselves are known as state functions because they only depend on the state of the system. However, dq and dw for example, are inexact ...
15
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1answer
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Why do methane molecules have 15 degrees of freedom?

I've just been learning a little thermal chemistry including the equipartition theorem. As part of this, my textbook discusses how to figure out the degrees of freedom for different chemicals. The ...
15
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4answers
657 views

Relative strength of desiccants

Is it meaningful to characterize the relative strength of desiccants? For example, is there a measure of hygroscopy, or an ordering of desiccants, such that higher ones will always dry lower ones? ...
15
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1answer
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Stability of organophosphorous vs organophosphates?

In environmental chemistry, most of the organophosphorous compounds we worry about are actually organophosphate compounds. Is there something about the $\ce{C-P}$ bond that makes it less stable (and ...
15
votes
2answers
4k views

Stoichiometric defects in silver bromide

Stoichiometric defects (Schottky and Frenkel defects) in ionic crystals are formed due to irregularities in the ionic arrangement which maintain the stoichiometry and electroneutrality of the solid. ...
14
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6answers
5k views

Is there a cheap, safe liquid that evaporates EXOthermically around room temperature?

The heating and AC system in the building where I occasionally work, works like this (basically a thermostat): The administrators set some temperature that is maintained automatically. Say, in the ...
14
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5answers
27k views

What is a pure substance?

I found as I was preparing to teach "Introduction to thermodynamics" that there are varying definitions or examples of pure substances. For instance the text book I have to use "Thermodynamics an ...
14
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2answers
45k views

When I heat up a balloon, does the air inside increase in pressure as well as volume?

When I heat up a balloon, does the air inside the balloon increase in pressure as well as volume? I thought pressure and volume were inversely proportional? Or does pressure and volume increase as ...
14
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3answers
2k views

Does an irreversible reaction have an equilbrium between reactants and products?

Retrospective analysis 2/13/2017 -- The barium sulfate example is a poor choice. Equilibrium equations should really be defined using activities, and the activity of solid barium sulfate is by ...
14
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1answer
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Why is there sulfur in black powder / gun powder?

Black powder is composed of charcoal, sulfur and a nitrate salt. The charcoal and sulfur serve as fuel and the nitrate is the oxidizing agent. However, wouldn't it be cheaper to leave out the sulfur,...
14
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3answers
3k views

Transition state and free energy

We have products $\ce{A + B}$ combining to form $\ce{C + D}$ through the transition state $\ce{X}$. Are all reactions at least virtually reversible? Is the difference between a reversible reaction ...
14
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2answers
6k views

Is the specific heat capacity of liquid iron constant?

Does liquid iron have a constant specific heat capacity? Everywhere I've looked (save one sourceless online reference to $c_p = 611\ \mathrm{J\ kg^{–1}\ K^{–1}}$ here), I find no value listed for ...
13
votes
3answers
202 views

Why can't a reaction go to completeness?

What is the reason for why an exergonic reaction would still have some remaining reactants (or an endergonic reaction to have any products)? The explanation given on this page (see Chemical reactions ...
13
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2answers
1k views

What causes spray cans to get cooler when shaken?

I've been searching the web for this phenomenon and surprisingly I found only one post about it. And the reply to this question about canned air begins with words: I don't know about the shaking ...