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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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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 ...
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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 \...
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4answers
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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 ...
27
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3answers
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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 ...
7
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3answers
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Can the change in internal energy be nonzero if temperature is constant?

I have learnt that internal energy, $U$, is a state function and it only depends on temperature... So if $\Delta T = 0$ then $\Delta U = 0$. However when I was studying exothermic and endothermic ...
9
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2answers
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Le Châtelier's Principle and heat

Consider the following reaction at equilibrium. $$\ce{A->B}, \Delta H < 0 $$ Suppose I increase the temperature. Now, quite a few people would invoke Le Châtelier's Principle and say that since ...
25
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4answers
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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 ...
11
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4answers
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Is there a reason for the mathematical form of the equilibrium constant? [duplicate]

Why are the two molarities multiplied and not added, and why is each raised to the power of the coefficient rather than multiplied by it? What is the reasoning behind this form? Was it simply ...
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 ...
33
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5answers
104k 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?
17
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2answers
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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 ...
20
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3answers
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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?
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2answers
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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 ...
98
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1answer
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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 ...
19
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1answer
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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 ...
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2answers
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Justification for Freezing Point Depression & Boiling Point Elevation in Solutions?

I was wondering if the following justification for freezing point depression and boiling point elevation are conceptually correct. The reason why I ask this question is because I have been self ...
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4answers
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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\...
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3answers
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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?
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1answer
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Why does the Gibbs free energy only correspond to non-expansion work?

It has been defined as the energy available for work other than expansion work. Why can't it be used for expansion work
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1answer
25k views

Reversible and Irreversible adiabatic expansion

A $\mathrm{200.0\ m^3}$ balloon at $253.0\ \mathrm K$ ascends to a higher altitude. If the initial pressure inside the balloon is $325$ millibar, and it ascends to a latitude with a pressure of $7.45$ ...
14
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3answers
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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 ...
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3answers
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How is Negative Temperature Hotter than Infinite Temperature?

Recently I have read articles stating that negative Kelvin has been achieved. I was a bit speculative at first as I though how can you get cold than 0 Kelvin, but after doing some research it makes ...
7
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1answer
15k views

Derivation of relationship between equilibrium constant and Gibbs free energy change

Why is $\Delta G=\Delta G^o+RT\ln Q?$ It feels like all online sources were written for introductory Chemistry students! Where do I find a rigorous proof of this identity? Greatly appreciate it!
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1answer
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What happens to water under high pressures without possibility of escape?

Knowing very little about the nature of water, wondering how it might behave at the centre of a planet or centre of an another massive gravitational body. Could water take such pressures or might it ...
8
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2answers
705 views

Comparing formula for enthalpy change with bond dissociation energy and formation enthalpy

I learnt that given a reaction: $$\ce{A -> B}$$ the enthalpy change is given by: $$\Delta H = \left( \begin{array}{c} \text{total enthalpy of}\\ \text{bonds broken}\end{array}\right)-\left( \begin{...
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5answers
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How can decreasing in temperature indicate an endothermic reaction?

I’m really wondering how can decreasing the temperature refer to an endothermic reaction. I faced this when I was calculating the heat of a reaction Q in a constant-pressure calorimeter. What I ...
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5answers
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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 ...
91
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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 ...
29
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4answers
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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 ...
20
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1answer
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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 $\ce{Na2Cl}$). ...
9
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2answers
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What exactly is a spontaneous reaction?

What I understand by a spontaneous reaction is that - A reaction whose G is negative and which occurs without the input of energy. Gasoline reacts with oxygen only if a spark is provided. So how can ...
14
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3answers
4k 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 ...
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4answers
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Why calcium chloride is used to melt ice over sodium chloride

I'm not quite sure I understand this. My question is: Calcium chloride is a salt used widely to melt ice on sidewalks and roads. Explain why one mole of $\ce{CaCl2}$ would be more effective than ...
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2answers
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Conditions for spontaneity

So the two conditions for a reaction to be spontaneous are: tendency to achieve minimum energy tendency to achieve maximum randomness. Both these things are contrasting and the only way I see them ...
2
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3answers
11k views

Spontaneous/Non-Spontaneous Reactions and Reversible Reactions

My chemistry textbook states "Reversible reactions constitute a limiting case between spontaneous and non-spontaneous processes." Does this mean that some of the reversible reactions are spontaneous ...
13
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2answers
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Why does N₂ react with O₂ to Form NO at high temperatures?

This also raises questions that I have about the Haber Process which produces ammonia ($\ce{NH3}$) from molecular nitrogen ($\ce{N2}$) and hydrogen ($\ce{H2}$). I have heard multiple times that bond ...
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1answer
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Why must both the critical temperature and pressure be exceeded to achieve the supercritical phase?

The characteristics and properties of supercritical fluids and the associated vapor-liquid critical point are well established. One thing that I've always been curious about, though: what is the ...
8
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1answer
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Why is N₂ stable but HCN and C₂H₂ unstable?

Compounds with triple bonds generally seem to be unstable. $\ce{HCN}$ and $\ce{C2H2}$ are high-energy, relatively short-lived molecules that will readily polymerise or react with other organic ...
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1answer
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Why does the equilibrium constant depend on the temperature but not on pressure and concentration?

According to my textbook (and intuitively) certain changes when the aforementioned 3 variables are altered occur in accordance with Le Chatelier's Principle. However, what I don't understand is what ...
2
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1answer
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Internal pressure of ideal gas

$$\left(\frac{\partial U}{\partial V}\right)_{\!T}$$ I know that this partial derivative is equal to zero for an ideal gas, but how do I determine that? Do I need to use the fundamental thermodynamic ...
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2answers
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Why does temperature affect cell potential?

The Nernst equation describes the relationship between cell potential and temperature. But why does temperature affect cell potential? My understanding is that the collision model of kinetics is not ...
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2answers
1k views

Spontaneity of Reactions- Gibbs Energy or Entropy change

I just wanted to check if I am thinking right: The reason why we consider the Gibbs energy to be the measurer for spontaneity of a reaction is because it does not depend whether the reaction was exo- ...
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3answers
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What is the difference between ΔG and ΔrG?

Consider the reaction $$\ce{A -> B}$$ The reaction Gibbs free energy, $\Delta_\mathrm{r} G$ is given by the following equation $$\Delta_\mathrm{r} G = \Delta_\mathrm{r} G^\circ + RT \ln Q$$ Now ...
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3answers
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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 ...
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3answers
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Relation between constant-pressure and constant-volume heat capacities: Cp - Cv = nR

For an ideal gas, we have $$C_p - C_V = nR$$ where $C_p$ is heat capacity at constant pressure, $C_V$ is heat capacity at constant volume, $n$ is amount of substance, and $R=8.3144598(48)\ \mathrm{J\...
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1answer
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Derivation of van 't Hoff equation for temperature dependence of equilibrium constant

While I was reading about the usefulness of the quantity $\Delta H$, I found that it can be used to calculate the how the equilibrium constant varies with temperature. How can this be done? Does it ...
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2answers
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Mathematical explanation behind dq = TdS

Can somebody mathematically prove why $$\mathrm dq = T\,\mathrm dS$$ for a reversible process? I realize I am supposed to provide some research but I can't find anything. The best I got is $\mathrm ...
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5answers
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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 $...
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2answers
47k 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 ...
13
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1answer
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Entropy - “Wiggle”?

The title is not a reference to a Jason Derulo song. In any case: 1) How is change in entropy measured, experimentally? I've Googled this for a bit and I've found all sorts of mathematical ...