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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45
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4answers
3k views

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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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 ...
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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 \...
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 ...
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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 ...
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 ...
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 ...
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 ...
101
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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 ...
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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 ...
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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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4answers
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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 ...
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5answers
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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?
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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 ...
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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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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 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 $\ce{Na2Cl}$). ...
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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?
9
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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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2answers
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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 $7.45$ ...
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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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1answer
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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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2answers
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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{...
12
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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 ...
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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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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 ...
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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 ...
10
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1answer
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Phosphorus standard state

Why is white phosphorus considered to be the standard state of phosphorus although it is only metastable? Red phosphorus is thermodynamically more stable than white phosphorus, yet it is not the ...
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4answers
93k 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 ...
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
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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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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 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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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 ...
4
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1answer
352 views

Le Chatelier's principle with pure solids and liquids

In the following reaction: $$\ce{A(s) <=> B(g) + C(g)}$$ since adding a pure solid is not supposed to shift the equilibrium in any way, does that mean that I can essentially remove all of the ...
8
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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 ...
5
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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 ...
24
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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 ...
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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 ...
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 ...
2
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1answer
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Thermodynamics and equilibrium constant [duplicate]

I just wanted to make sure how we can know whether it is $K_c$ (equilibrium constant of concentrations) or $K_p$ (equilibrium constant of pressures) which "comes out" of the equation, $\Delta G^o= -RT ...
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 ...
2
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3answers
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Is a liquid in a container always in equilibrium with its vapour?

This is essentially a question about the meaning and significance of the term vapour pressure (or vapor pressure if you're American). From what I understand a liquid in a container will have a certain ...
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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 ...
5
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3answers
4k views

Why do we use the external pressure to calculate the work done by gas

I read in a textbook that in the case when we have a gas in a cylinder fitted with a massless frictionless piston being held with an external pressure $p_1$, and when the pressure is reduced to become ...
5
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2answers
620 views

Why does equilibrium exist?

I've read an article that equilibrium exists when $G$ (Gibbs free energy) becomes minimum. If formation of products decreases Gibbs free energy, why won't the reaction proceed to completion so that ...
3
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2answers
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What is the correct definition of the Gibbs free energy of activation?

Is the following correct? Gibbs free energy of activation is used in energy profiles where the stabilities of the species are expressed as changes in Gibbs energy, while the activation energy Ea is ...
3
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4answers
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Since the formation of diamond from Graphite is endothermic and the entropy decreases for this process, how is it possible to make diamond?

Surely G would always be positive and thus would make it impossible to make diamond. Clearly this is not the case. But how? Would an increase or decrease in temperature aid it's formation? I think a ...
2
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1answer
174 views

How is heat physically released in an exothermic process?

Many non-covalent interactions (e.g. electrostatic interactions) result in decreased entropy and are driven by negative enthalpy. If the heat released in the reaction has its physical basis in an ...
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2answers
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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- ...