Questions tagged [physical-chemistry]

The study of chemical systems using the laws and concepts of physics. This usually requires the techniques of thermodynamics, statistical mechanics and quantum mechanics.

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Does aromaticity require a co-planar pi system?

It's well established that angular twisting can decrease the degree of delocalization across a $\pi$ system (e.g. biphenyl). Moreover, there's considerable debate about aromaticity in spherical ...
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What should the Rehm-Weller equation look like?

The Rehm-Weller equation, which defines the energy change for photoinduced electron transfer according to Lakowicz "Principles of Fluorescence Spectroscopy" [1, p. 337] should look like: $$\Delta G=E^...
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What is the opposite of a surfactant?

Surfactants decrease surface tension between two fluids. What do you call a substance that increases the surface tension between two fluids? How is this effect acheived?
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Le Chatelier's principle: Are there any exceptions?

The way Le Chatelier's principle is presented in most introductory chemistry books (high-school) is as though it's an indisputable law of the physical world (in the sense that we're never shown an ...
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Why are the total energies of transition states so commonly corrected for zero-point vibrational energy?

So often I see total energies of transition states corrected for zero-point vibrational energy which always confuses me. Zero point energy is the lowest energy that a ground state minimum energy ...
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What are the major factors that influence LogP

The partition coefficient is a very useful metric in characterizing compounds particularly drugs. What chemical properties influence that partitioning? Are chemical moieties additive in their LogP? ...
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Why does like dissolve like?

Polar solvents love polar solutes to be dissolved in it and non polar with non polar. Often said as like dissolves like. Okay, polar loving polar can be understood with help of the facts: same polar ...
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Why does small value of van der Waals gas constant “b” ensure easier liquefication?

Larger value of b signifies that the size of the molecules is larger and hence the forces acting should become larger due to increased surface area.This should ensure easier liquefication. But my book ...
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Why do some gases have lower value of Z for a particular pressure?

In the above graph,the minima of the curve for methane is more than that of nitrogen. Also, for a given value of pressure, the value of $Z$ for methane is less than that of nitrogen. They seem to meet ...
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Explaining Ionization to kids

I have a quest to explain a physical, chemical theory to kids of age 8-12. The topic is "Ionization". We all understand from early experiments of Physics and Chemistry (the Millikan oil drop ...
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What causes the lowering of vapour pressure in volatile/nonvolatile solvent mixtures?

"Based on Figure 13.18, you might think that the reason volatile solvent molecules in a solution are less likely to escape to the gas phase, compared to the pure solvent, is that the solute molecules ...
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How do electronegativity and lone pairs affect bond angles?

How do bond angles vary in molecules with a lone pair and central atom of different electronegativity, but in the same period so that electronegativity matters more than orbital size? Let's assume ...
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Verifying data acquired from a molecular dynamics simulation

This question is about verifying a system simulated with MD. I am currently building a model of a two phase gas-liquid system, where I initially have $\ce{N2}$, $\ce{CO2}$, $\ce{Ar}$, $\ce{He}$ and $\...
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How to calculate partition coefficients?

Below is a transcript of this doubtful question: A weak monobasic organic acid $\ce{HA}$ is soluble in both water and $\ce{CHCl3}$. $\pu{500.0 cm3}$ of a solution of $\ce{HA}$ in $\ce{CHCl3}$, ...
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Calculating Triplet-Triplet Spin-Orbit Coupling

According to the Q-Chem manual [1], the singlet-triplet spin-orbit couplings between a singlet excited state $I$ and a triplet excited state state $J$ is: $$\langle\Phi_\text{singlet}^I|\hat{\mathrm H}...
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How do I excel in Chemistry? [closed]

I wanted to ask an online group of experts/community about how I could improve in chemistry. I study in 10th grade currently and don't get very good grades. Most of the time its a B or C. I have to ...
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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=N_\mathrm A\cdot k_\...
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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 ...
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Why does the C–C bond have extremely weak absorptions?

My book, Pavia's Introduction to Spectroscopy, tells me this about the infrared spectrum of alkanes: $\ce{C-C}$ : Stretch not interpretatively useful; many weak peaks. This is very interesting. ...
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Do Electrons Really 'Spin'?

With regard to the 'Electron Spin Number', lots of websites mention that electrons don't really spin and that the electron spin number has nothing to do with any physical spinning. However, my ...
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Can you heat water with additives?

I have been curious about this question for a while. If you want to warm up a large amount of water, is it feasible to do this by adding a substance that has an exothermic reaction with the water? ...
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Why exactly does precipitation occur?

In a solution, we have ions floating around but when we have a precipitate, they're arranged as they would be in a solid. This conversion should cause a decrement in the entropy of the system and ...
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758 views

By what mechanisms can molecules with the same empirical formula be so different?

I understand the difference between empirical and chemical formula. But I always thought that compounds and molecules took their specific shape because it's the lowest energy configuration. How then, ...
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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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Which materials/compounds expand in response to cold temperatures?

Which materials or compounds expand in response to cold temperatures? This material or compound should expand at a slow (but constant rate), from about 0–20 months when in the following temperature ...
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Negative Kelvin Temperature

I remember my Physical Chemistry Professor saying that very tiny negative Kelvin temperatures have been achieved on the quantum level. Is this true?
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Destabilization of antibonding MO vs stabilization of bonding MO

My textbook writes that The net energy stabilization due to the occupation of a bonding MO is equal to the net energy destabilization due to the occupation of the corresponding antibonding MO. ...
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What's the difference between perfect and ideal gas?

There are all kinds of different dinstinctions in the internet, and I'd like to see what you guys thought. Actually, I've been asked if the heat capacity of an ideal gas es independent of temperature....
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Why is the Maxwell–Boltzmann formula inapplicable at low temperatures?

This Wikipedia article states that at sufficiently low temperatures (or high pressure), quantum effects lead to a breakdown of Maxwell–Boltzmann statistics. I know that the spacing of energy levels ...
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Does gravity affect the trajectory of gas particles?

We're studying the kinetic theory of gases in school, and one of the points that was brought up was that: "Gases consist of particles in constant, random motion." How is it possible for gas particles ...
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Why search new elements?

I've read this today. From the little I know, they discover new elements by bombarding some atoms in particle accelerators (I guess) and these new elements last a few miliseconds. So what's the ...
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Why is the specific heat of water high?

How is the specific heat of water so high? I was reading the hyperphysics article on it but could not understand it properly.
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Terminology of atomic spectroscopy: Difference Among Term, States and Level

In A Primer on Quantum Numbers and Spectroscopic Notation Contents, the concept of a term and level is described as a) The level is the set of 2J+1 states with specific values of L, S, and J. ...
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Why are indicators used only in the form of dilute solutions?

Why are indicators used only in the form of dilute solutions? I get that indicators are a form of weak acids themselves, and the extent of their dissociation varies with the pH of the solution they ...
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Difference between Reaction Rate and Rate Law?

Lets say you have the reaction $$\ce{$a$A + $b$B -> $c$C + $d$D}$$ The rate of the reaction is given by the change in initial concentration over the change in time. $$-\frac{\Delta \left[\ce A \...
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How does absorption spectroscopy work?

So a beam of white-light photons passes through a gas and various photons, having exactly the same energy as the gas's molecular energy transition state deltas, get absorbed. We then get a ...
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Free chemical database to search for physical properties?

I am looking for an Open-access tool that can search "backwards", eg. give me all the structures corresponding to a given heat of formation, critical pressure, etc. It would be even better if the ...
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What does “correct orientation” in a chemical reaction mean conceptually?

My chemistry teacher was talking about how there are two requirements for a reaction to occur: The reactants must have enough energy; and they must also have the correct orientation for a reaction ...
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Acidity of hydrochloric acid in acetic acid

A question asked to find the $\mathrm pK_\mathrm a$ of $\ce{HCl}$ in acetic acid. The equation of $\ce{HCl}$ disassociating in water is: $$\ce{HCl + CH3COOH \leftrightharpoons CH3COOH2+ + Cl-}$$ I ...
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Maximum temperature attainable by thermite reaction

In the thermite reaction $$\ce{2Al(s) + Fe2O3(s) -> 2Fe(l) + Al2O3(s)}$$ what is the maximum temperature attainable by the products? Assume reactants at $25\ \mathrm{^\circ C}$ and $1\ \mathrm{...
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995 views

Flory–Schulz type distribution with stoichiometric imbalance

In a typical step-growth polymerization, the Anderson–Schulz–Flory distribution is the probability mass function that describes the number fraction or weight fraction of polymers of length $x$ at a ...
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Explanation of bond angles in the aluminium chloride dimer

In order to attain stability $\ce{AlCl3}$ dimerises to $\ce{Al2Cl6}$ whose structure is depicted as: I want to understand why one of the bond angles is $79^\circ$ and the other $118^\circ$. Is it ...
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Why is the melting point of tert-butyl alcohol 140 °C higher than that of sec-butyl alcohol?

This is one of the most drastic differences in a physical property I've ever seen for two such similar molecules, and in a simplistic sense anyway the difference lies in the opposite direction from ...
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Relationship between magnitudes of forward and reverse kinetic rate constants

Consider the reversible unimolecular reaction: $$\ce{A <=>[k_1][k_2] B}$$ We know that the forward reaction is often considerably more thermodynamically favourable than the reverse reaction, ...
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How to simulate surface tension?

I am trying to create a water drop simulation for measuring hydrophobicity of surface. I don't know how to simulate the contact angle which is related by younges equation to the surface tensions for ...
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119 views

What equipment is used for two-dimensional IR spectroscopy and how can the molecular structure of a compound be resolved?

On the Wikipedia page about two-dimensional IR spectroscopy it is said that 2D IR spectroscopy can be used to study the molecular dynamics with femtosecond time resolution. According to Wikipedia ...
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Estimating stability and mean life of anomalous tautomers

A pair of bases in the DNA, say, A-T, have a tautomerized form A*-T* (resulting from switching the sides of both protons along the hydrogen bridges). I have studied how, by means of DFT computations, ...
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Why do 3d orbitals have lesser energy than 4s orbitals in transition metals? [duplicate]

This is quoted from Jim Clark's Chemguide For reasons which are too complicated to go into at this level, once you get to scandium, the energy of the 3d orbitals becomes slightly less than that of ...
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Why do diamond and graphite have different structures, when they are both composed of carbon?

Both diamond and graphite are covalent networks and are both made entirely from carbon, but why does diamond have a three dimensional network of strong covalent bonds which makes it hard, whereas ...
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Chemical properties of isotopes

I've always heard that different isotopes of the same element have exactly the same chemical properties. But for example, I've read that some compounds which have hydrogen atoms interchanged by ...