Prisoner of Azkaban
Ron’s picture in the Daily Prophet with Scabbers, because of
Arthur's winning the prize and setting off for Egypt,
precipitates Sirius’s breakout and subsequent break-in at
Hogwarts.
After the Trio meets up in Diagon Alley, they take Scabbers to
the pet store for some medicine. The owner is shocked that an
average rat has lived so long.  Our first clue that something's
up.)

Crookshanks makes a mad dive for Scabbers, but Ron just thinks
Crooks hates him. Hermione buys Crookshanks. Thus the main
contention between the pair is created from the first day they
meet after not seeing each other all summer.
    “What was that?”
    "It was either a very big cat or quite a small
tiger,” said Harry.
    “Where’s Hermione?”
    ...
Her arms were clamped tightly around the enormous ginger
cat.
    “You bought that monster?”
    “He’s gorgeous, isn’t he?” said Hermione,
glowing.
    ...
    “Hermione, that thing nearly scalped me!” said
Ron.
    “He didn’t mean to, did you, Crookshanks?” said
Hermione.
Prisoner of Azkaban
Chapter 4
Their fighting reaches an all time high in this book.

Ron is awful to Hermione all throughout the book because he thinks
Crookshanks is trying to eat Scabbers and he blames Hermione for
that and is infuriated when she stands up for her cat.
(Ron rushes to Scabbers defense and is
obviously upset by the rat’s “death”. Yet
he always said he hated his pet. Perhaps
this is how Ron shows affection.

(The more he hates you, the more he
harasses you and makes fun of you equals
the more he likes you.

(But, then, shouldn’t we hope for more for
Hermione.

(Oh, I don’t know, perhaps a nice boy, not
one who calls you names and makes you feel
bad all the time? I can’t imagine Rowling
hates Hermione that much to pair her with
Ron.)
In fact, Ron reacts worse than Harry does when she tells
Professor McGonagall about the broom. Between the Firebolt
incident and the "death" of Scabbers, he goads Harry into not
speaking to her (Harry was angry, but not to that extent, even
when Harry and Hermione have been the most at odds with each
other they’ve never even gone a whole day without speaking).  
    "OY!" Ron roared, seizing his bag as
Crookshanks sank four sets of claws deep inside it and
began tearing ferociously. "GET OFF, YOU STUPID ANIMAL!"
    Ron tried to pull the bag away from
Crookshanks, but Crookshanks clung on, spitting and
slashing.
    "Ron, don't hurt him!" squealed Hermione; the
whole common room was watching; Ron whirled the bag
around, Crookshanks still clinging to it, and Scabbers
came flying out the top -
    ...
    "There's something funny about that animal!"
said Ron, who was trying to persuade a frantically
wiggling Scabbers back into his pocket. "It heard me say
Scabbers was in my bag!"
    "Oh, what rubbish," said Hermione impatiently.
    ...
..."And Scabbers was here first, and he's ill!"
Ron marched through the common room and out of sight...
Ron was still in a bad mood with Hermione the next day.
He barely talked to her.
Prisoner of Azkaban
Chapter 8
Scabbers and Crookshanks are images of their owners. They don't
get along and we hear Ron's sentiments, for himself and Hermione
as much for the pets, "Scabbers was here first."

Scabbers (or Ron) has more right and a better status because they
were here first. Hermione/Crookshanks came along later making
them less important, less worthy.
Scabbers Vs. Crookshanks
Ron jumps at the chance to show that he’s the “better friend” and
I think here we see the final break of Ron from trying to talk
any amount of sense into Harry to just agreeing with everything
he says. Ron is trying to gain an edge over Hermione.

He takes the first opportunity he can get to push Hermione away.
Ron no doubt is hoping that this will be the final break and
Harry will see that Ron is the better friend after all.
Harry knew that Hermione had meant well, but that didn't
stop him from being angry with her.

...Ron was furious with Hermione too. As far as he was
concerned, the stripping-down of a brand-new Firebolt
was nothing less than criminal damage.
Prisoner of Azkaban
Chapter 11
    "I said I wonder what's wrong with Lupin, and you -"
    "Well, isn't it obvious?" said Hermione, with a look
of maddening superiority.
    "If you don't want to tell us, don't" snapped Ron.
    "Fine," said Hermione haughtily, and she marched off.
    "She doesn't know," said Ron, staring resentfully
after Hermione. "She's just trying to get us to talk to
her again."
Prisoner of Azkaban
Chapter 12
I'm sorry, what does Ron have to do with it anyway? What reason
does he have not to talk to Hermione? It wasn't his Firebolt.

It is Harry who has to initiate reconciliation or else Ron would
have gone on not speaking to her even after the Firebolt was
returned.
    "She gave it to you? Excellent! Listen, can I still
have a go on it?  Tomorrow?"
    "Yeah...anything...," said Harry, his heart lighter
than it had been in a month. "You know what - we should
make up with Hermione...She was only trying to help..."
    ...
    "I got it back," said Harry, grinning at her and
holding up the Firebolt.
    "See, Hermione? There wasn't anything wrong with it!"
said Ron.
    "Well - there might have been!" said Hermione. "I
mean, at least you know now that it's safe!"
    "Yeah, I suppose so," said Harry. "I'd better put it
upstairs -"
    "I'll take it!" said Ron eagerly.
    ...
    "Can I sit down, then?" Harry asked Hermione.
    "I suppose so," said Hermione, moving a great stack
of parchment off her chair.
Prisoner of Azkaban
Chapter 12
Unfortunately, Ron is about to find out Scabbers has been killed.
When he finds the blood stains he immediately runs back down to
the common room to accuse Hermione of wrong-doing.

They haven't spoken to her in over a month and now Ron sets about
not speaking to her again.

Both he and Harry forget their promise to help with Buckbeak's
case. Everything is left for Hermione to shoulder, and even with
her workload, she does so.
It looked like the end of Ron and Hermione's friendship.
Each was so angry with the other that Harry couldn't see
how they'd ever make up.
    ...
Personally, Harry was sure that Crookshanks had eaten
Scabbers, and when he tried to point out to Hermione
that the evidence all pointed that way, she lost her
tempter with Harry too.
    "Okay, side with Ron, I knew you would!" she said
shrilly. "First the Firebolt, now Scabbers, everything's
my fault, isn't it!"
Prisoner of Azkaban
Chapter 13
He blames Hermione for Crookshanks “attacking” Scabbers and only
the impending doom of Buckbeak snaps him out of his egocentric
self-concern.  When it’s too late, then he finally takes action.
He tries to help after the verdict is in.

In fact, it is Hagrid who is left to scold the boys for their
treatment of Hermione. She has been completely abused in this
novel.
    "She's cried a fair few times, yeh know. Goin'
through a rough time at the moment. Bitten of more'n she
can chew, if yeh ask me, all the work she's tryin' ter
do. Still found time ter help me with Buckbeck's case,
mind..."
    "Hagrid, we should've helped as well - sorry - "
Harry began awkwardly.
    ...
    "I gotta tell yeh, I thought you two'd value yer
friend more'n broomsticks or rats. Tha's all."
    Harry and Ron exchanged uncomfortable looks.
    "Really upset, she was, when Black nearly stabbed
yeh, Ron. She's got her heart in the right place,
Hermione has, an' you two not talkin' to her - "
Prisoner of Azkaban
Chapter 14
Ron's too busy stewing about how Hermione won't stop defending
Crookshanks and proving to Harry that he's much more fun than
Hermione.

He persuades Harry to sneak into Hogsmeade again. (Hermione once
again is left as the voice of reason and tries to persuade them
against the idea.)

Snape catches Harry and almost confiscates the Marauder's Map.
Lupin tells Harry that leaving himself open to the mercy of a
madman like Black is a "poor way to repay" his parents.

Ron feels guilty, as he should.
    "It's all my fault," said Ron abruptly. "I persuaded
you to go. Lupin's right, it was stupid, we shouldn't
have done it -"
    He broke off; they reached the corridor where the
security trolls were pacing, and Hermione was walking
toward them.
    ...
    "Come to have a good gloat?" said Ron savagely as she
stopped in front of them. "Or have you just been to tell
on us?"
    "No," said Hermione. She was holding a letter in her
hands and her lip was trembling. "I just thought you
ought to know...Hagrid lost his case. Buckbeak is going
to be executed."
Prisoner of Azkaban
Chapter 14
So even though Ron acknowledges he did something wrong, he
attacks Hermione as soon as he sees her. He doesn't stop to ask
what she wants or even notice that she's near tears.

This is two times he realizes too late that he was in the wrong.
And for anyone who believes in 'it's better late then never', I
remind you that's it's not better for Buckbeak. And it wouldn't
have been better for Harry, who would have surely been expelled
if Snape had his way.
Ron, Prisoner of Azkaban
They go down to be with Hagrid because they know he’s
upset about Beaky. They go to him; they seek him out
to comfort him. In the process, they find the
presumed dead Scabbers, which leads to yet another
fight between Ron and Hermione causing Hagrid to
intervene yet again.  
This makes it even harder for me to believe that they
would all turn around 3 years later and not only NOT
be there for Hagrid when he directly asked for them,
but actively avoid him.  It wasn’t that they couldn’t
make it; they just didn’t want to be bothered.
Ron chases Scabbers to the Whomping Willow, and then
gets dragged inside to the Shrieking Shack. This
prompts Harry and Hermione to follow after and the
revelation that Scabbers is Peter Pettigrew.
Another similarity to Neville here: Neville was used to motivate
action in Book 1 and here in Book 3, Ron suits the same purpose.
(For additional similarities, see
Neville.)
Despite being hurt, Ron produces his one shining moment, when he
is literally willing to sacrifice himself for Harry.
    Without knowing what he was doing, he started
forward, but there was a sudden movement on either side
of him and two pairs of hands grabbed him and held him
back..."No, Harry!" Hermione gasped in a petrified
whisper; Ron, however, spoke to Black.
    "If you want to kill Harry, you'll have to kill us
too!" he said fiercely, though the effort of standing
upright was draining him of still more color, and he
swayed slightly as he spoke.
He did so figuratively in the first book, but here he declares
that if Sirius and Lupin want to kill Harry they’ll have to kill
him first.  (Not very imposing as he can’t even stand up, but
still, it’s the thought that counts.)

Ron shows his true friendship is to Harry – he’s willing to do
anything for Harry, even risk injury or worse.  (Yet he isn’t
around for the more complicated, dangerous part [i.e. – Dementors
by the lake (Hermione & Sirius); going back in time (Hermione)].)
I also find it funny that he volunteers Hermione for the job as
well. It is just understood that she'd sacrifice herself for
Harry as well.
Prisoner of Azkaban
Chapter 17
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