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Prevention
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Start treating your little dog like a dog from the day you get him. Make sure you socialize him by taking him around people. Let them handle him and let him walk around the people. Socialize him around other dogs, too. Take him to puppy classes or to homes of friends who own dogs. Let them sniff each other and, if the other dog is not too large or overbearing, play together. Train your puppy. An obedient dog will automatically be well-behaved and become more secure, not feeling the need to bite.
Puppies
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Puppies bite and chew. They bite as they play, as they establish dominance. They chew because it's fun and because they are teething. This is normal. As cute as it seems, do not let them chew and bite on your hands; they may come to view this as acceptable. Instead, provide them with many toys. When your Chihuahua puppy begins you use your hand as a bone, firmly correct him by saying "no biting" and provide him with a toy as an alternative. But make sure you supervise your puppy as he chews on a toy. You don't want him choking on small pieces that may fall off.
An Older Dog
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What if your dog has already established himself as King Goliath? Don't worry, you can still do something about it. You have an advantage over a little dog--you can pick him up. If your little dog snaps at you or another person, pick him up, lay him gently on his back, and firmly tell him "no." This move puts him into a submissive position, which establishes you as the leader. At first, your Chihuahua may not feel comfortable with this situation, but over time, he will come to accept your new status and feel more secure.
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Tips on Training a Chihuahua From Nipping
If you've ever owned little dogs such as Chihuahuas, you know that they are unlike larger breeds, partly because you treat them differently. When they jump up on you upon your return home, it's cute--so you don't correct them. You carry them around under your arm and let them curl up in your lap. When they first begin snapping, you don't treat it seriously--after all ... they're so small. So they become king of the castle. But you can--and should--avoid that.